Polymer production

ABSTRACT

A method for producing a polymeric material, said method comprising subjecting a starting material which includes two multiple bonds which are activated so that they will take part in a polymerisation reaction and wherein the multiple bonds are sufficiently close togeter to ensure that cyclopolymerisation will preferentially occur; to suitable conditions under which said polymerisation reaction will occur, provided that the starting marerial is other than triallyamine hydrochloride. The method can be used to produce polymers for various processes including adhesives, network polymers, liquid crystal polymers etc.

The present invention relates to methods of producing polymericcompounds, in particular using radiation curing such ultraviolet orthermal radiation, or chemical curing or electron beam initiated curing.Certain compounds which form polymers under the influence of u.v. lightform a further aspect of the invention, as well as to polymers, coatingsand adhesives obtained thereby.

The polymerisation of diallyamines using free radical initiation isknown, for example from Solomon et al., J. Macromol. Sci.- Rev Macromol.Chem. c15 (1) 143-164 (1976). Free radical initiation of polymerisationrequires quite extreme reaction conditions which can be generated onlyin production plants etc. It is not suitable for situations where insitu polymerisation is required.

Other cyclpolymerisation reactions are discussed by C. D. McLean et al.,J. Macromol. Sci.-Chem., A10 (5), pp857-873 (1976). Yet furtherreactions are described in WO 97/16504, WO97/16472 where such reactionsare used in a specialised way in the production of liquid crystalcompounds.

The applicants have found that a broad range of compounds with at leasttwo appropriately positioned multiple bonds and in particular doublebonds may be activated by the presence of an electron withdrawing group,in particular where the electron withdrawing group is at a positionwhich is alpha, beta or gamma to one or both of the double bonds to makethem readily polymerisable under the influence of inter alia radiation.The term “readily polymerisable” means that the compounds will undergopolymerisation under moderate conditions of temperature and pressure(for example at room temperature and atmospheric pressure) in thepresence of radiation and an initiator, in a period of less than 24hours.

Polymeric compounds obtained therefrom include cyclic rings. These havemany advantageous properties. In particular, the invention can be usedto generate products such as adhesives (see copending British Patentapplication No 9816169.8), coatings, network polymers or conductingpolymers (see copending British Patent Application No. 9816171.0)depending upon the other aspects of the structure of the startingmaterials.

In its broadest aspect, the invention provides a method for producing apolymeric material, said method comprising subjecting a startingmaterial which includes two double bonds which are activated so thatthey will take part in a polymerisation reaction and wherein the doublebonds are sufficiently close together to ensure that cyclopolymerisationwill preferentially occur; to suitable conditions under which saidpolymerisation reaction will occur, provided that the starting materialis other than triallyamine hydrochloride.

Specifically, the invention provides a method for producing a polymericmaterial, said method comprising subjecting a starting material whichcomprises a group of sub-formula (I)

where

R¹ is CR^(a) where R^(a) is hydrogen of alkyl, and R⁶ is a bond, or R¹and R⁶ together form an electron withdrawing group;

R² and R³ are independently selected from (CR⁷R⁸)_(n), or a groupCR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸ areindependently selected from hydrogen or alkyl, and either one of R⁹ orR¹⁰ is hydrogen and the other is an electron withdrawing group, or R⁹and R¹⁰ together form an electron withdrawing group, and

R⁴ and R⁵ are independently selected from CH or CR¹¹ where R¹¹ is anelectron withdrawing group;

the dotted lines indicate the presence or absence of a bond, and X¹ is agroup CX²X³ where the dotted line bond to which it is attached is absentand a group CX² where the dotted line bond to which it is attached ispresent, Y¹ is a group CY²Y³ where the dotted line bond to which it isattached is absent and a group CY² where the dotted line bond to whichit is attached is present, and X², X³, Y² and Y³ are independentlyselected from hydrogen and fluorine;

provided that at least one of (a) R¹ and R⁶ or (b) R² and R³ or (c) R⁴and R⁵ includes an electron withdrawing group which is able to activatea cyclopolymerisation reaction; to suitable conditions under which acyclopolymerisation reaction will occur, subject to the followingfurther provisos:

(i) that the starting material is other than triallyamine hydrochloride;

(ii) that when R¹ and R⁶ together form the sole electron withdrawinggroup and R¹ is a group N⁺R¹² (Z^(m−))_(1/m), where R¹² is hydrogen orhydrocarbyl, Z is an anion of charge m and R⁶ is a bond, said conditionsare subjecting the compound to radiation in the substantial absence of asolvent or sulphur dioxide gas; and

(iii) that where R¹ and R⁶ together form the sole electron withdrawinggroup and R¹ is CH and R⁶ is OC(O), then the compound does not furthercontain a mesogenic group, or contains at least one further group ofsub-formula (I).

As used herein, the expression “in the substantial absence of solvent”means that there is either no solvent present or there is insufficientsolvent present to completely dissolve the reagents, although a smallamount of a diluent may be present to allow the reagents to flow.

Conditions under which polymerisation will occur include the influenceof radiation or an electron beam, or in the presence of a chemicalinitiator. Radiation or electron beam induced polymerisation is suitablyeffected in the substantial absence of a solvent.

In particular X¹ and Y¹ are groups CX²X³ and CY²Y³ respectively and thedotted lines represent an absence of a bond. Thus preferred compoundsare those of sub-formula (IA)

where R¹, R², R³, R⁴, R⁵, R⁶, X², X³, Y² and Y³ are as defined above.One or more such starting materials may be polymerised together. Whenmore than one starting material is used, a copolymer will result.

When the dotted bonds in sub formula (I) are present, the resultingpolymer will comprise polyacetylene chains. This can lead to aconjugated system and consequently a conducting polymer.

Suitably there are no more than five atoms in between or linking thedouble bonds in the starting material so that when thecyclopolymerisation takes place, for example as illustrated hereinafterin FIG. 1, the size of the rings formed does not exceed 7. Preferably,there are from 3 to 5 atoms in between the double bonds.

Suitably the starting material is one which will cyclopolymerise in thesort of conditions used in polymer production. This may comprise theapplication of radiation such as uv or thermal radiation, wherenecessary in the presence of a photoinitiator, by the application ofother sorts of initiator such as chemical initiators, or by initiationusing an electron beam. The expression “chemical initiator” as usedherein refers to compounds which can initiate polymerisation such asfree radical initiators and ion initiators such as cationic or anionicinitiators as are understood in the art.

Preferably, the starting materials polymerise under the influence ofultraviolet or thermal radiation, preferably ultraviolet radiation.Cyclopolymerisation may take place either spontaneously or in thepresence of a suitable initiator. Examples of suitable initiatorsinclude 2,2′-azobisisobutyronitrile (AIBN), aromatic ketones such asbenzophenones in particular acetophenone; chlorinated acetophenones suchas di- or tri-chloroacetophenone; dialkoxyacetophenones such asdimethoxyacetophenones (sold under the Trade name “Irgacure 651”);dialkylhydroxyacetophenones such as dimethylhydroxyacetophenone (soldunder the Trade name “Darocure 1173”); substituteddialkylhydroxyacetophenone alkyl ethers such compounds of formula

where R^(y) is alkyl and in particular 2,2-dimethylethyl, R^(x) ishydroxy or halogen such as chloro, and R^(p) and R^(q) are independentlyselected from alkyl or halogen such as chloro (examples of which aresold under the Trade names “Darocure 1116” and “Trigonal P1”);1-benzoylcyclohexanol-2 (sold under the Trade name “Irgacure 184”);benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers inparticular benzoin butyl ether, dialkoxybenzoins such asdimethoxybenzoin or deoxybenzoin; dibenzyl ketone; acyloxime esters suchas methyl or ethyl esters of acyloxime (sold under the trade name“Quantaqure PDO”); acylphosphine oxides, acylphosphonates such asdialkylacylphosphonate, ketosulphides for example of formula

where R^(z) is alkyl and Ar is an aryl group; dibenzoyl disulphides suchas 4,4′-dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone;4,4′-bis(N,N-dialkylamino)benzophenone; fluorenone; thioxanthone;benzil; or a compound of formula

where Ar is an aryl group such as phenyl and R^(z) is alkyl such asmethyl (sold under the trade name “Speedcure BMDS”)

As used herein, the term “alkyl” refers to straight or branched chainalkyl groups, suitably containing up to 20 and preferably up to 6 carbonatoms. The term “alkenyl” and “alkynyl” refer to unsaturated straight orbranched chains which include for example from 2-20 carbon atoms, forexample from 2 to 6 carbon atoms. Chains may include one or more doubleor triple bonds respectively. In addition, the term “aryl” refers toaromatic groups such as phenyl or naphthyl.

The term “hydrocarbyl” refers to any structure comprising carbon andhydrogen atoms. For example, these may be alkyl, alkenyl, alkynyl, arylsuch as phenyl or napthyl, arylalkyl, cycloalkyl, cycloalkenyl orcycloalkynyl. Suitably they will contain up to 20 and preferably up to10 carbon atoms. The term “heterocylyl” includes aromatic ornon-aromatic rings, for example containing from 4 to 20, suitably from 5to 10 ring atoms, at least one of which is a heteroatom such as oxygen,sulphur or nitrogen. Examples of such groups include furyl, thienyl,pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl,oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl,pyridazinyl, triazinyl, quinolinyl, iosquinolinyl, quinoxalinyl,benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.

The term “functional group” refers to reactive groups such as halo,cyano, nitro, oxo, C(O)_(n)R^(a), OR^(a), S(O)_(t)R^(a), NR^(b)R^(c),OC(O)NR^(b)R^(c), C(O)NR^(b)R^(c), OC(O)NR^(b)R^(c), —NR⁷C(O)_(n)R⁶,—NR^(a)CONR^(b)R^(c), —C═NOR , —N═CR^(b)R^(c), S(O)_(t)NR^(b)R^(c),C(S)_(n)R^(a), C(S)OR^(a), C(S)NR^(b)R^(c) or —NR^(b)S(O)_(t)R^(a) whereR^(a), R^(b) and R^(c) are independently selected from hydrogen oroptionally substituted hydrocarbyl, or R^(b) and R^(c) together form anoptionally substituted ring which optionally contains furtherheteroatoms such as S(O)_(s), oxygen and nitrogen, n is an integer of 1or 2, t is 0 or an integer of 1-3. In particular the functional groupsare groups such as halo, cyano, nitro, oxo, C(O)_(n)R^(a), OR^(a),S(O)_(t)R^(a), NR^(b)R^(c), OC(O)NR^(b)R^(c), C(O)NR^(b)R^(c),OC(O)NR^(b)R^(c), —NR⁷C(O)_(n)R⁶, —NR^(a)CONR^(b)R^(c),—NR^(a)CSNR^(b)R^(c), —C═NOR^(a), —N═CR^(b)R^(c), S(O)_(t)NR^(b)R^(c),or —NR^(b)S(O)_(t)R^(a) where R^(a), R^(b) and R^(c), n and t are asdefined above.

The term “heteroatom” as used herein refers to non-carbon atoms such asoxygen, nitrogen or sulphur atoms. Where the nitrogen atoms are present,they will generally be present as part of an amino residue so that theywill be substituted for example by hydrogen or alkyl.

The term “amide” is generally understood to refer to a group of formulaC(O)NR^(a)R^(b) where R^(a) and R^(b) are hydrogen or an optionallysubstituted hydrocarbyl group. Similarly, the term “sulphonamide” willrefer to a group of formula S(O)₂NR^(a)R^(b).

AS described above, suitable starting materials for use in the method ofthe invention will comprise a group of sub-formula (I)

where

X¹, X², Y¹ and Y² are independently selected from hydrogen or fluorine,R¹ is CR^(a) where R^(a) is hydrogen or alkyl, and R⁶is a bond, or R¹and R⁶ together form an electron withdrawing group;

R² and R³ are independently selected from (CR⁷R⁸)_(n), or a groupCR⁹R¹⁰, —(CR⁷R⁸CR⁹R¹⁰)— or —(CR⁹R¹⁰CR⁷R⁸)— where n is 0, 1 or 2, R⁷ andR⁸ are independently selected from hydrogen or alkyl, and either one ofR⁹ or R¹⁰) is hydrogen and the other is an electron withdrawing group,or R⁹ and R¹⁰ together form an electron withdrawing group, and

R⁴ and R⁵ are independently selected from CH or CR¹¹ where R¹¹ is anelectron withdrawing group;

provided that at least one of (a) R¹ and R⁶ or (b) R² and R³ or (c) R⁴and R⁵ includes an electron withdrawing group.

The nature of the electron withdrawing group or groups used in anyparticular case will depend upon its position in relation to the doublebond it is required to activate, as well as the nature of any otherfunctional groups within the compound.

In a preferred embodiment, R¹ and R⁶ form an electron withdrawing group.For example, R¹ is a heteroatom or a substituted heteroatom which haselectron withdrawing properties, for example a group N⁺R¹²(Z^(m−))_(1/m), S(O)_(p)R³ , B, P(O)_(q)R¹⁴ or Si(R¹⁵) where R¹², R¹³,R¹⁴ and R¹⁵ are independently selected from hydrogen or hydrocarbyl, Zis an anion of charge a, p is 0, 1 or 2, and q is 1; and R⁶ is a bond:or R¹ is a group CH and R⁶ is a group —C(O)O— or —OC(O)—. Mostpreferably, R¹ is a group N⁺R¹² (Z^(m−))_(1/m), S(O)_(p)R¹³, B,P(O)_(q)R¹⁴ or Si(R¹⁵) where R¹², R¹³, R¹⁴ and R¹⁵ are independentlyselected from hydrogen or alkyl in particular C₁₋₃ alkyl, and Z is ananion, preferably a halide. In particular R¹ is a group N⁺R¹²(Z^(m−))_(1/m), and R⁶ is a bond.

The nature of the anion Z will affect the properties of the finalpolymer and in particular, its conductivity, porosity and waterpermability. Suitable anions for the Z group include halide ions such asfluoride, chloride, bromide or iodide, borides such as borontetrafluoride; carboxylic acid esters such as those of formula R¹⁴C(O)O—where R¹⁴ is an optionally substituted hydrocarbyl group group such ashaloalkyl, in particular trifluoromethyl; and other cationic groups suchas mesylate and tosylate. In general, the water permeability of theultimate polymer will vary as follows:

PF₆ ⁻<BF₄ ⁻<CF₃SO₃ ⁻<CF₃COO⁻<NO₃ ⁻<SO₄ ²⁻<I⁻<Br⁻<Cl⁻

Other factors which affect the water permeability of the polymer is thenature of any group to which the group of sub-formula (I) is attached.When this contains for example perhaloalkyl substituents such asperfluoroalkyl, it will be largely water impermeable as compared topolymers which have alkylene bridging groups optionally interposed withsay oxygen. Examples of such groups are given below.

Most preferably, the combination of R¹ and R⁶ forms an amide group,where R¹ is a nitrogen atom and R⁶ is a carbonyl group. In a furtherpreferred embodiment, R¹ and R⁶ together form a sulphonamide group whereR¹ is a nitrogen atom and R⁶ is an S(O)₂ group.

Alternatively, where the activation is effected by electron withdrawinggroups at a position indicated by R² or R³, suitable electronwithdrawing groups R⁹ and R¹⁰ include nitrile, trifluoromethyl, acylsuch as acetyl or nitro, or preferably R⁹ and R¹⁰ together with thecarbon atom to which they are attached form a carbonyl group.

Where R¹¹ is an electron withdrawing group, it is suitably acyl such asacetyl, nitrile or nitro.

Preferably X¹, X², Y¹ and Y² are all hydrogen.

Suitable groups R^(a) include hydrogen or methyl, in particularhydrogen.

A preferred group of the compounds for use in the method of theinvention is a compound of structure (II)

and in particular a compound of formula (IIA)

where X¹, X², X³, Y¹, Y², Y³, R¹, R², R³, R⁴, R⁵, R⁶ and the dottedbonds are as defined in relation to formula (I) above, r is an integerof 1 or more, and R¹⁶ is a bridging group, an optionally substitutedhydrocarbyl group, a perhaloalkyl group or an amide, of valency r.

Where in the compound of formula (II) and (IIA), r is 1, compounds canbe readily polymerised to form a variety of polymer types depending uponthe nature of the group R¹⁶ and examples of groups which are commonlyfound in polymer technology is included below in Table 1. Some may beable to act, for example, as radiation curable adhesives as described incopending British Patent application No 9816169.8.

However, other applications for such polymers obtained using the processof the invention may be found.

Monomers of this type may be represented as structure (III)

where X¹, X², Y¹, Y², R¹, R², R³, R⁴, R⁵ and R⁶ are as defined inrelation to formula (I) above, R¹⁶ is an optionally substitutedhydrocarbyl group, a perhaloalkyl group or an amide.

Preferably in the compounds of formula (III), as above, R¹ and R⁶ forman electron withdrawing group. Suitably then R² and R³ are groups(CR⁷R⁸) n and R¹ and R⁵ are CH groups. Suitably, in the case ofadhesives, R¹⁶ comprises a hydrocarbyl group, optionally substituted bya functional group. Preferably R⁷ includes an unsaturated moiety, suchas an aryl or alkenyl group, or a carbonyl substituent.

A class of compounds of formula (III) are those of formula

where R⁶ is as defined above, and is in particular an optionallysubstituted alkyl, alkenyl, alkynyl or aryl group, wherein the optionalsubstituents may be selected from halogen, hydroxy, carboxy or saltsthereof or acyloxy. These compounds may be used in the monomer form asadhesive compositions. However, pre-formed polymers obtained bypolymerisation of these monomers form an aspect of the presentinvention.

Alternatively, R^(16′) in formula (IV) may comprise a perhaloalkylgroup, for example of from 1 to 3 carbon atoms such as a perhalomethylgroup, in particular perfluoromethyl. Another group for R^(16′) informula (IV) is a dialkenyl substituted amide, for example of subformula (V)

where R¹⁸ and R¹⁹ are selected from groups defined above for R² and R³in relation to formula (I), and are preferably —CH₂— or —CH₂CH₂— groups;and R²⁰ and R²¹ are selected from groups defined above as R³ and R⁴ inrelation to formula (I) and are preferably —CH— groups. Such groupswould further activate the double bonds and give rise to the possibilityof forming cross-linked polymer networks.

Another class of compound of formula (II) is represented by radiationcurable compounds of formula (VI)

where Z and m are as defined above, R²² and R²³ are independentlyselected from hydrogen and hydrocarbyl, such as alkyl and alkenyl, inparticular prop-2-enyl or hydroxyethyl.

The invention may also be applied to other sorts of polymers, forexample, where in the compounds of formula (II), r is greater than one,polymerisation can result is polymer networks. Particular examples arecompounds of formula (II) as defined above, where R¹⁶ is a bridginggroup and r is an integer of 2 or more, for example from 2 to 8 andpreferably from 2-4.

On polymerisation of these such compounds, networks are formed whoseproperties may be selected depending upon the precise nature of the R¹⁶group, the amount of chain terminator present and the polymerisationconditions employed. Polymerisation will occur in accordance with thegeneral scheme set out in FIG. 1 hereinafter.

Suitably r is an integer of from 2 to 6, preferably from 2 to 4. Thepolymers produced can be useful in a number of different applicationsincluding the production of network polymers and those used in thermalmanagement. Such applications are described and claimed in copendingBritish Patent application No. 9816171.0.

Thermal management is the control of optical properties of materialsacross solar and thermal wavebands (˜0.7-12microns). This control oftransmitted, reflected and absorbed radiation gives the potential todesign systems that can selectively perform different tasks at differentwavelengths. For example use of silver coatings by the glazing industryto limit solar transmission (material transparent at visible wavelengthsbut reflective across the solar) and thus prevent ‘greenhouse’ heating.Other example could be solar water heaters where the material istransparent at NIR wavelengths but reflective at longer wavelengths.Benefits of thermal management could be in reduced airconditioning/heating costs.

The properties of the polymer obtained in this way will depend upon avariety of factors but will depend very largely on the nature of thegroup R¹⁶.

Suitably R¹⁶ will comprise a bridging groups for example as is known inpolymer, paint or coating chemistry. These may include straight orbranched chain alkyl groups, optionally substituted or interposed withfunctional groups or siloxane groups such as alkyl siloxanes. Suitablebridging groups include those found in polyethylenes, polypropylenes,nylons, as listed in Table 1.

TABLE 1 Polymer type Repeat Unit of Bridging Group Polyethylene CH₂Polystyrene CH₂CH(C₆H₅) where the phenyl ring is optionally substitutedPolyisobutylene CH₂CH(CH(CH₃)₂) Polyisoprene Ch₂CH(CH₃)Polytetrafluoroethylene CH₂(CF₂)_(x)CH₂ PolyvinylidenefluorideCH₂(CF₂CH₂)_(x) polyethyleneoxide (OCH₂CH(CH₃))_(x)O NylonCH₂(NHCOCH₂)_(x)CH₂ Peptide CH₂(NHCOCH_(R))_(x)CH₂ Polyurethanes—NH—CO—O— Polyesters —RC(O)OR′— where R and R′ are organic groups suchas hydrocarbyl Polysiloxanes e.g. —SiO₂—, —R₂SiO— or —R₂Si₂O₃— where Ris an organic group such as hydrocarbyl Polyacrylates —CH₂C(COOH)H—Polyureas —NHCONH— Polythioureas —NH—C(S)—NH—

The length of the bridging group will affect the properties of thepolymeric material derived from this. This can be used to designpolymers with properties which are best suited to the application. Forinstance when the bridging group comprises relatively long chains, (forexample with in excess of 6 repeat units, for example from 6-20 repeatunits), the polymer will have pliable plastic properties. Alternatively,when the bridging group is relatively short, (e.g. less than 6 repeatunits) the material will be more brittle.

Another method for producing particular properties arises from thepossibility of producing copolymers where another monomeric compound,for example one which is not of formula (I), is mixed with the compoundof formula (I) prior to polymerisation. Such monomers are known in theart.

Composites may also be produced by polymerising compounds of formula (I)in the presence of other moieties such as graphite, ethers such as crownethers or thioethers, phthalocyanines, bipyridyls or liquid crystalcompounds, all of which will produce composite polymers with modifiedproperties.

Examples of possible bridging groups R¹⁶where r is 2 are groups ofsub-formula (VII)

—Z¹—(Q¹)_(a)—(Z²—Q²)_(b)—Z³—  (VII)

where a and b are independently selected from 0, 1 or 2, z₁, Z² and Z³are independently selected from a bond, an optionally substituted linearor branched alkyl or alkene chain wherein optionally one or morenon-adjacent carbon atoms is replaced with a heteroatom or an amidegroup, Q¹ and Q² are independently selected from an optionallysubstituted carbocylic or heterocyclic ring which optionally containsbridging alkyl groups.

Suitable carbocyclic rings for Q¹ and Q²include cycloalkyl groups forexample from 1 to 20 carbon atoms. Bridged carbocylic ring structuresinclude 1,4-bicyclo[2.2.2] octane, decalin, bicyclo[2.2.1]heptane,cubane, diadamantane, adamantane. Suitable heterocyclic rings includeany of the above where one or more non adjacent carbon atoms arereplaced by a heteroatom such as oxygen, sulphur or nitrogen (includingamino or substituted amino), or a carboxyl or an amide group. Suitableoptional substitutents for the groups Q¹ and Q² include one or moregroups selected from alkyl, alkeny, alkynyl, aryl, aralkyl such asbenzyl, or functional groups as defined above. Substitutents for thegroups Q¹ and Q² are oxo and halogen in particular fluorine andchlorine.

Suitable optional substituents for the alkyl and alkene groups Z¹, Z²and Z³ include aryl, aralkyl and functional groups as defined above.Particular substituents include halogen such as fluorine and chlorine,and oxo.

Other sorts of bridging groups R¹⁶ include electrically conductingchains, for instance, electrically conducting unsaturated chains such asalkenes or chains incorporating aromatic or heterocyclic rings. Forinstance, the group R¹⁶ may comprise a tetra substituted conducting unitsuch as a tertathiafulvalene. Thus an example of such a is a compound offormula (VIII)

where R²⁸, R²⁹, R³⁰ and R³¹ are each groups of sub-formula (IX)

where R¹, R², R³, R⁴, R⁵ and R⁶ are as defined in relation to formula(I) above and R²⁴, R²⁵, R²⁶ and R²⁷ are independently selected fromgroups of sub-formula (II) as given above. In particular R²⁴, R²⁵, R²⁶and R²⁷ are alkyl groups.

Polymerisation of compounds of formula (III) will give cross-linkednetworks where the cross-linking occurs through the double bonded units.This will lead to a very stable material with robust physicalproperties. Once again, varying the length of the spacer groups R²⁴,R²⁵, R²⁶ and R²⁷ will lead to materials with designer properties. Forinstance when R²⁴, R²⁵, R²⁶ and R²⁷ are relatively long chains, thepolymer will have pliable plastic properties. Alternatively, when thechains R²⁴, R²⁵, R²⁶and R²⁷ are relatively short, the material will bemore brittle.

Where R¹ and R⁶ together form a group —N′R⁷Z⁻, varying the counter ion Zcan also be used to adjust the physical properties of the polymer, suchas water retention, porosity or conductivity. Suitably substitutedmaterials will exhibit conducting properties, making them suitable asorganic semiconductors for example for use as interconnects for IC chipsetc.

Alternatively, a bridging group R¹⁶ may comprise a tetra or octasubstituted non-linear optic unit such as an optionally substitutedporphyrin or phthalocyanine wherein the optional substitutents includehydrocarbyl groups as well as groups of sub formula (I). An example ofsuch a porphyin compound is a compound of formula (X)

where R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰ and R³¹ are as defined inrelation to formula (III) above and R³², R³³, R³⁴ and R³⁵ are eachindependently selected from hydrogen or hydrocarbyl groups; and thecompound optionally contains a metal ion within the macrocyclicheterocyclic unit.

An alternative phthalocyanine compound is a compound of formula (XA)

where R⁵⁰ through to R⁶⁵ are independently selected from hydrocarbyl inparticular C₁₋₁₂ alkyl, a group OR⁶⁸ where R⁶⁸ is hydrocarbyl inparticular butyl, halogen in particular chlorine or a group R²⁴-R²⁸where R²⁴ and R²⁸ are as defined in relation to formula (III) above,provided that at least two of R⁵⁰ to R⁶⁵ are R²⁴-R²⁸ groups, and R⁶⁶ andR⁶⁷ are either hydrogen or together comprise a metal ion such as acopper ion.

Preferably in formula (XA), R⁵¹, R⁵², R⁵⁵, R⁵⁶, R⁵⁹, R⁶⁰, R⁶³ and R⁶⁴are halogen and R⁵⁰, R⁵³, R⁵⁴, R⁵⁷, R⁵⁸, R⁶¹, R⁶² and R⁶⁵ areindependently C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy or a group R²⁴-R²⁸

Polymerisation of a compound of formula (X) or (XA) in accordance withthe scheme of FIG. 1, for example by photopolymerisation will provide across linked network polymer where the cross linking occurs through thediene units for example as either quaternery ammonium salts or amidesdepending upon the particular nature of the groups R¹ and R⁶ present inthe R²⁸, R²⁹, R³⁰ and R³¹ units. Again this can produce a very stablenetwork or elastomeric material with robust physical properties. Inaddition to conductivity, these polymers will be capable of exhibitingthird order polarisabilities and be suitable for applications whichemploy the Kerr effect. These properties can be affected or moderatedwhen metals or metal ions are inserted into the macrocyclic heterocyclicunit. Suitable metal ions include sodium, potassium, lithium, copper,zinc or iron ions.

Yet a further possibility for the bridging group R¹⁶ is a polysiloxanenetwork polymer where R¹⁶ comprises a straight or branched siloxanechain of valency r or a cyclic polysiloxane unit.

Thus compounds of structure (XI)

where R²⁴, R²⁵, R²⁸ and R²⁹ are as defined above in relation to formula(VII), R³², R³³, R³⁴ are R³⁵, are selected from hydrocarbyl such asalkyl and in particular methyl, and each R³⁶ or R³⁷ group isindependently selected from hydrocarbyl or a group of formula R⁶-R³⁰where R²⁶ and R³⁰ are as defined above in relation to formula (VII), andu is 0 or an integer of 1 or more, for example of from 1 to 20; and(XII).

where R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰ and R³¹ are as defined above inrelation to formula (VII) and R³², R³³, R³⁴ and R³⁵ are as defined abovein relation to formula (XI). Although formula (XII) has been illustratedwith four siloxane units in the ring, it will be appreciated that theremay be other numbers of such units in the cyclic ring, for example from3 to 8, preferably from 3 to 6 siloxane units.

In the above structures (XI) and (XII), it will be appreciated that —Si—may be replaced by B or B⁻; or —Si—O— is replaced by —B—N(R³⁹)— whereR³⁹ is a hydrocarbyl group such as those defined above in relation togroup R³² in formula (XI) or a group —R²⁴-R²⁸ as defined in relation toformula (XII) above.

Upon polymerisation, compounds of formula (XI) and (XII) or variantsthereof, will form a cross-linked network where the cross-linking occursthrough the groups R²⁸, R²⁹, R³⁰ and R³¹ as illustrated in FIG. 1. Suchpolymers may exhibit properties similar to those of conventionalsiloxanes. However, in the case of compounds of formula (XI) and (XII),they may be coated onto surfaces and polymerised in situ, for exampleusing radiation curing.

Further examples of compounds of formula (III) include compounds offormula (XIII)

where R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, R³⁰ and R³¹ are as defined above inrelation to formula (VIII).

The methodology of the invention may also be applied to the productionof liquid crystal polymers. In this case, the monomeric units willinclude a mesogenic group as is understood in the art.

For example, suitable polymers may be obtained by the polymerisation ofcompounds of formula (III) where R^(16 ′) comprises a group of subformula (XIV)

R³³—Z⁶—R²⁴—  (XIV)

where R²⁴ is as defined above, Z⁶ is selected from O, S, single covalentbond, COO, OCO; and R³³ represents any mesogenic group;

Compounds of this type are novel and form the subject of a copendingpatent application of the applicants.

Compounds of formula (II) are suitably prepared by conventional methods,for example by reacting a compound of formula (XV)

where X¹, Y¹, Y², R², R², R³, R⁴, R⁵ and the dotted bonds are as definedin relation to formula (II), R^(1′) is a group R¹ as defined in formulaII or a precursor thereof, and R⁴⁰ is hydrogen or hydroxy, with acompound of formula (XVI)

R¹⁶—[R⁶—Z⁴]_(r)  (XVI)

where R⁶, R¹⁶ and r are as defined in relation to formula (II) and Z⁴ isa leaving group, and thereafter if necessary, converting a precursorgroup R^(1′) to a group R¹.

Where a compound of formula (IIA) is produced, the compound of formula(XV) will be of formula (XVA)

where R^(1′), R², R³, R⁴, R⁵, R⁴⁰, X², X³, Y² and Y³ are as definedabove.

Suitable leaving groups Z⁴ include halogen in particular bromo, mesylateor tosylate. The reaction is suitably effected in an organic solventsuch as tetrahydrofuran, dichloromethane, toluene, an alcohol such asmethanol or ethanol, or a ketone such as butanone and at elevatedtemperatures for example near the boiling point of the solvent.

Preferably the reaction is effected in the presence of a base such aspotassium carbonate.

When the group R^(1′) is a precursor of the group R¹, it may beconverted to the corresponding R¹ group using conventional techniques.For example R^(1′) may be a nitrogen atom, which may be converted to agroup NR¹² (Z^(m−))_(1/m) where R¹², Z and m are as defined above, byreaction with an appropriate salt under conventional conditions.Examples of this are illustrated hereinafter.

Compounds of formulae (XV) and (XVI) are either known compounds or theycan be prepared from known compounds by conventional methods.

During the polymerisation process, the compounds link together by way ofthe multiple bond, in particular the diene group as illustrated inFIG. 1. Where the compounds used include more than one diene grouping,for example compounds of formula (II) where R is 2 or more, they willtend to become cross linked to form a network or three dimensionalstructure. The degree of cross linking can be controlled by carrying outthe polymerisation in the presence of cross-linkers, where for example ris greater than 2, for example 4, or diluents. The latter will suitablycomprise a compound of formula (XVI)

where X¹, X², Y¹, Y², R¹, R², R³, R⁴, R⁵, R⁶, R¹⁶ and r are as definedin relation to formula (II).

The method of the invention can be used in the preparation ofhomopolymers or copolymers where they are mixed with other monomericunits, which may themselves be of a similar basic structure, for exampleof formula (II) or otherwise.

A general scheme illustrating the sort of polymerisation process whichmay occur using a polyethylene type bridging group is illustrated inFIG. 2.

Using the method of the invention, it is possible to take a suitableorganic system that has optimal or optimised properties for use incertain applications, e.g. high yield strength, largehyperpolarisability, high pyroelectric coefficient, high conductivityetc. and to structurally modify the system so that it is possible topolymerise it. If functional groups are incorporated that willpolymerise, it will become possible to create a three dimensionalnetwork or plastic that will have properties associated with the parentorganic system.

The advantages of the compounds of the invention is that they allow forthe possibility that they can be applied in the form of a paint andcaused to polymerise in situ. Thus this allows for ease of processing.Further, by providing for the construction of networks as a result ofthe cross linking, the resultant polymer can be mechanically strong anddurable.

The versatility of the systems of the invention mean that it is possibleto build in anisotropy which would improve directional physicalproperties, e.g. NLO, mechanical yield strength etc. Both amorphous orordered systems can be prepared depending upon the particularpolymerisation conditions used.

Copolymerisation is also possible and this can be used advantageously toaffect physical properties of the polymer obtained.

Polymers obtained using the method of the invention maybe particularlysuitable for the production of adhesive coatings, and multilayercoatings as well as binders. It is possible to manipulate the low molarmass coating before polymerisation is carried out, e.g., poling etc.

Films of polymeric material can be prepared as illustrated hereinafter.Thus material with the properties of for example, polyethylene films canbe produced using radiation curing techniques if required.

Polymer coatings prepared as described herein have usefulwater-proofing, corrosion resistance and general dust and dirtprotective properties, in particular where they include halogenated andparticularly fluorinated bridging groups. Thus they may be used in theproduction of fabrics such as clothing, electrical components ordevices, mechanical components as well as building materials whichrequire this feature. In addition, coatings of this type may produceanti-icing features which are useful, particularly where these materialsare exposed to harsh external conditions. Products treated in this wayalso exhibit strong pearling qualities and this assists in the rapidshedding of condensate. Thus surfaces remain relatively free of suchcondensates.

Such surfaces can be achieved on at least part of the internal surfacesof a structure containing interconnecting interstitial spaces, such asfibrous or granular material. The present invention provides a productselected from a fabric, an electrical component or device, a mechanicalcomponent, or a construction or building material, having depositedthereon a polymeric coating derived from a monomer of formula (I) asdefined above.

Suitable electrical components include small electrical components suchas resistors, capacitors, condensers, circuit breakers, switches andconnectors, as well as small assemblies of these, for example circuitboards on which these and/or other components are mounted. Electricaldevices include conductors, such as HT leads for example, those used inautomobile engines, and cables such as external or underground powercables. Such cables may be pre-coated with plastics of anotherinsulating material.

Plastics coatings in accordance with the invention may be applied toelectrical wiring. In particular, monomers of formula (I) which mimicpolypropylene would be useful in this context.

Mechanical components include housings, bearings, shafts, gears, wheels,gaskets, filter housing, engines, gearboxes, transmission, steering orsuspension components.

Building materials include wood, brick, concrete slabs or otherpre-formed concrete structures, building blocks, stone, slates orinsulation materials where there is a possibility that corrosion,weathering or water penetration is likely to cause problems.

Polymer coatings formed in accordance with the invention may be usefulin electronic components which have a polymeric coating as resistancelayers. The nature of the bridging group R¹⁶ will affect the resistanceof the polymer layer.

Optionally the bridging groups in the monomers may be aromatic orheteroaromatic, i.e. it may include one or more unsaturated carbonrings, optionally containing heteroatoms such as nitrogen, oxygen orsulphur, which give the surface formed additional resistance to etchingby plasma etch processes as used in the semiconductor integrated circuitindustry.

If necessary, the coating may be discontinuous, for example, patternedby etching, optionally after masking certain areas, so as to provide thedesired electronic properties. Techniques for achieving this are wellknown, and include for example, irradiation with high energy radiationsuch as electron beams, X-rays or deep ultraviolet rays.

The irradiation breaks the bonds in the polymer and exposed areas canthen be dissolved in a developer liquid. Optionally, the coating mayconsist of a mixture of a monomer and a chemical designed to enhance itssensitivity to radiation exposure during the patterning process, such asquinione diazide or anthraquinone.

Suitable electronic components include printed circuit boards,semiconductor elements, optical devices, videodiscs, compact discs,floppy discs and the like.

The invention will now be particularly described by way of example withreference to the accompanying diagrammatic drawings in which:

FIG. 1 illustrates the polymerisation in accordance with the method ofthe invention; and

FIG. 2 shows a general scheme whereby cross-linking to form networkpolymers may occur.

EXAMPLE 1

Diallylamine (6.45 g, 0.66 mol), 1,10-dibromodecane (10.0 g, 0.033 mol)and potassium carbonate 9.70 g, 0.66 mol) were placed in ethanol (60cm³) and the mixture was refluxed for 10 hours. The solids were removedby filtration and the solvent removed in vacuo to leave a yellow oil.The oil was purified by column chromatography using silica gel and ethylacetate to leave, after removal of solvent in vacuo, 9.80 g, 89% ofyellow oil.

¹HNMR (CDCl₃) δ: 1.15-1.30 (m, 12H), 1.35-1.45 (m, 4H), 2.40 (t, 4H),3.10 (d, 8H), 5.05-5.20 (m, 8H), 5.30-5.55 (m, 4H).

Ir νmax (thin film): 2920, 2850, 2800, 1640, 1460, 1440, 1350, 1250,1150, 1110, 990, 915 cm⁻¹.

The monomer from step 1 above (4.0 g) was treated with 3M aqueousmethanolic trifluoroacetic acid to pH 1.0. The organic phase wasextracted with dichloromethane (100 cm³) and washed with brine (60 cm³)and water (60 cm³) and then dried over MgSO₄. Removal of solvent left ayellow oil. 6.4 g, 95%.

¹HNMR (CDCl₃) δ: 1.30 (m, 12H), 1.65 (quin, 4H), 3.0 (quin, 4H), 3.72(s, 8H), 5.60 (m, 8H), 5.90 (m, 4H), 10.10 (s, 2H).

Ir νmax (KCl disc): 2934, 2861, 1780, 1669, 1428, 1169.3 (s), 994.5,950.8, 798, 722, 706, 617 cm⁻¹.

The monomer from step 2 above (0.2 g) and Irgacure 184 (5 mg) weredissolved in dry dichloromethane (2 cm³) and the solution. was spreadevenly on a 18×25 cm glass plate. The solvent was evaporated off toleave a thin film. It was then irradiated with a Philips UVA sunlamp (75w) for 10 minutes. The resultant cross-linked polymer was removed asstrips (scalpel), washed in dichloromethane (50 cm³ ) and thoroughlydried. Yield 0.1 g, 50%.

Ir νmax (KCl disc): 2940, 2864, 1780, 1650, 1428, 1170, 995, 951, 799,743, 722, 620 cm⁻¹.

EXAMPLE 2

The monomer obtained in Example 1 step 1 (5.0 g) was treated with a 3Maqueous methanolic solution of hexafluorophosphoric acid (3.0 m) to pH1.The PF₆ ⁻ salt was extracted using dichloromethane (2×100 cm³) and thecombined extracts were dried over MgSO₄. Removal of solvent left ayellow oil. 9.16 g, 96%.

Ir νmax (KCl disc): 3508, 3199, 2931, 2859, 2663, 1691, 1648, 1469, 427,1290, 1142, 1049, 996, 953, 842.6 (s), 737 cm⁻¹.

¹HNMR (CDCL₃) δ: 1.25 (s, br, 12H), 1.65 (s, br, 4H), 2.95 (s, br, 4H),3.65 (s, br, 8H), 5.60 (m, 8H), 5.90 (m, 4H), 9.75 (s, br, 2H).

The monomer from step 1 (0.2 g) was dissolved with Irgacure 184 (5 mg)in dry dichloromethane (1.0 cm³) and the solution spread evenly on a 2×4sq″ sheet of aluminium. The solvent was removed by warming and the filmwas irradiated with the Philips UVA (75 w) u/v lamp for 10 minutes toform a cross-linked polymeric coating.

Ir νmax: 3434, 2937, 2859, 2717, 1674, 1467, 1297, 1140, 843 (s) (P−F),558 cm⁻¹.

EXAMPLE 3

The monomer from Example 1 step 1 (1.0 g) was treated with 3M aqueousmethanolic hydrochloric acid to pH 1.0 (universal indicator paper). Theorganic phase was extracted with dichloromethane (100 cm³) and washedwith brine (60 cm³) then water (60 cm³) and dried over MgSO₄. Removal ofsolvent left a heavy yellow oil. 1.2 g, 96%.

Ir νmax (KCl. Disc): 2929, 2855, 2632, 2536, 1645, 1456, 1426, 1362,1222, 997, 948 cm⁻¹.

¹HNMR (DMSO) δ: 1.25 (m, 10H), 1.67 (m, 4H), 2.89 (m, 4H), 3.66 (s, 8H),5.42-5.53 (m, 8H), 5.96-6.01 (m, 4H), 11.20 (s, 2H).

The diallylamine salt obtained in step 1 above (1.0 g, 0.0025 mol) andIrgacure 184 (25.3 mg, 0.000124 mol) were dissolved in drydichloromethane (2 cm³) and the solution spread on an 18×25 cm² glassplate. The solvent was allowed to evaporate and the remaining clear filmwas irradiated for approximately 3 minutes under a Philips UVA (75 w)sunlamp. The resultant cross-linked polymer was removed from the glassplate, washed in dichloromethane and. Yield 0.75 g, 775%.

Ir νmax (KCl disc): 2800-2200 (broad), 1620 (w), 1455 (s), 1050 (w),1000 (w), 950 (w), 720 (w) cm⁻¹.

EXAMPLE 4

The monomer obtained as described in Example 1 step 1 (3.0 g, 0.0094mol) and methyl iodide (2.60 g, 0.22 mol) in dry dichloromethane (30cm³) were refluxed together for 7 hours. The solvent and residual methyliodide were removed in vacuo and the orange residue re-dissolved in drydichloromethane (100 cm³). The orange solution was washed in brine (50cm³) and dried over MgSO₄. Removal of solvent gave an orange oil whichformed a soft solid on standing. Yield 4.95 g, 89%.

¹HNMR (DMSO) δ: 1.27 (m, 12H), 1.69 (m, 4H), 2.99 (6H), 3.10-3.20 (m,4H), 3.95 (d, 8H), 5.55-5.75 (m, 8H), 5.95-6.18 (m, 4H).

Ir νmax (KCl disc): 3081, 2925, 2854, 2361, 1689, 1641, 1470, 1424,1371, 1302, 1246, 994, 943, 894, 868, 724, 6.68.

Step 1A

In an alternative preparation of the compound of step 1 above, themonomer obtained as described in Example 1 step 1 above (10.0 g, 0.030mol) and methyl iodide (9.23 g, 0.065 mol) in a mixture oftetrahydrofuran (100 cm³) and dichloromethane (20 cm³) were stirredtogether. After 0.5 hour the solution began to become turbid and theturbidity increased as time progressed. The solvent was removed in vacuoand the white solid residue was suspended in 40/60 petrol (100 cm³) andstirred for 1 hour. Filtration and thorough drying in vacuo gave 17.79g, 96% of a white, soft solid.

¹HNMR (CDCl₂) δ: 1.20-1.40 (s, 12H), 1.80 (s, 4H), 3.20 (s, 6H), 3.40(m, 4H), 4.15 (m, 8H), 5.65-5.86 (m, 8H), 5.95-6.10 (m, 4H).

Ir νmax (KCl disc): 3080, 3050, 2930, 2860, 1640, 1470, 1440, 1425,1370, 1300, 995, 945 cm⁻¹.

The monomer from step 1 above (0.7 g, 0.00114 mol) and Irgacure 184(23.2 mg, 0.00014 mol) were dissolved in dry dichloromethane (3 cm³).The monomer/photoinitiator mixture was spread evenly on an 18×25 cm³glass plate and the solvent left to evaporate in air to leave a clear,light yellow film. The film was irradiated with a Philips UVA (75 w)sunlamp for 15 minutes. Examination showed that the monomer hadpolymerised to form a hard, cross-linked polymer. The polymer wasremoved as strips of clear film and placed in dry dichloromethane (100cm³) and the mixture stirred for 15 minutes. The film strips wereremoved by filtration and dried in vacuo.

Ir νmax (KCl disc): 2923, 2852, 1680 (w), 1613, 1461 (s), 950 (s), 726cm⁻¹.

A similar reaction using 1.0 g(0.0016 mol) of the monomer obtained instep 1A above and 16.3 g (0.00008 mol) Irgacure 184 produced 0.84 g(84%) of cross-linked polymer.

Ir νmax (KCl disc): 3480 (H₂₀), 2920, 2860, 1640 (w), 1460, 1000, 955cm⁻¹.

EXAMPLE 5

3,6,9-Trioxaundecandioic Acid (4.4 g, 0.0179 mol), 1,4-pentadien-3-ol(3.0 g, 0.0357 mol), 1,3-dicyclohexylcarbodiimide (7.63 g, 0.037 mol)and 4-dimethylaminopyridine (250 mg) were stirred together in drydichloromethane (100 cm³) for 48 hours at room temperature. The1,3-dicyclohexylurea was removed by filtration and the, solvent removedin vacuo to leave an oil. Purification using silica gel and ethylacetate—40:60 petrol (1:1) as eluent followed by removal of solvent andthorough drying gave 6.4 g, 91% of colourless, clear oil.

Ir νmax (thin film): 2920, 2860, 1750, 1635, 1420, 1380, 1350, 1270,1250, 1195, 1150, 1120, 990, 935, 880, 850, 730, 690, 580 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.65-3.80 (m, 8H), 4.15 (s, 4H), 5.25-5.50 (m, 10H),5.75-5.95 (m, 4H).

The monomer from Example 5 step 1 (1.5 g, 0.0042 mol) and Irgacure 184(43 mg) were dissolved in dry dichloromethane (2 ml) and the solutionwas spread evenly on an 18×25 cm plate glass sheet. The solvent wasallowed to dry in air then the remaining polymer/photoinitiator film wasirradiated beneath a Philips UVA (70 w) U/V sunlamp for 2 hours. Theresultant cross-linked polymer was scraped (scalpel) from the plate andsuspended in dry dichloromethane (20 ml) and the suspension was stirredfor approximately 15 minutes. The polymer was recovered by filtrationand the retained solid washed with dry dichloromethane (2×16 cm³) andthen dried thoroughly to leave 0.6 g 40% of clear film polymericmaterial.

Ir νmax (thin film): 2920, 2860, 1740, 1630, 1450, 1380, 1275, 1200,1145, 1120, 850 cm⁻¹.

EXAMPLE 6

3,6,9-Trioxaundecandioic acid (5.33 g, 0.024 mol), 1,5-Hexadien-3-ol(5.0 g, 0.051 mol), 1,3-dicyclohexylcarbodiimide (10.5 g, 0.051 mol) and4-dimethylaminopyridine (250 mg) were stirred together in drydichloromethane (50 cm³) at room temperature for 6 hours. The1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to leave a yellow oil which was purified by columnchromatography using silica gel/ethyl acetate. Yield 8.0 g, 87%.

¹HNMR (CDCl₃) δ: 2.4 (t, 4H), 3.65 (m, 8H), 4.20 (s, 4H), 5.05-5.45 (m,10H), 5.65-5.90 (m, 4H).

Ir νmax (thin film): 2920, 2860, 1760, 1640, 1425, 1200, 1150, 1120,990, 920 cm⁻¹.

The monomer from step 1 above (1.6 g, 0.0042 mol) and Irgacure 184 (43mg, 5 mol%) were dissolved in dry dichloromethane (2 ml) and thesolution was spread evenly on an 18×25 cm plate glass sheet. The solventwas allowed to dry in air then the remaining polymer/photoinitiator filmwas irradiated beneath a Philips UVA (70 w) U/V sunlamp for 2 hours. Theresultant cross-linked polymer was scraped (scalpel) from the plate landsuspended in dry dichloromethane (20 ml) and the suspension was stirredfor approximately 15 minutes. The polymer was recovered by filtrationand the retained solid washed with dry dichloromethane (2×10 cm³) andthen dried thoroughly to leave a clear film polymeric material. Yield1.34 g, 87%.

Ir νmax (thin film): AWH/11: 2920, 2860, 1740 (S), 1635, 1450, 1430,1380, 1280, 1200, 1145, 1120, 990, 925, 850 CM−1.

EXAMPLE 7

3,6,9-Trioxaundecanoic acid (5.0 g, 0.026 mol), diallylamine (5.10 g,0.055 mol), 1,3-Dicyclohexylcarbodiimide (11.35 g, 0.055 mol) and4-dimethylaminopyridine,(0.5 g) were stirred together in drydichloromethane (100 cm³) for 6 hours. The resultant1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to give a yellow oil. Column chromatography using ethylacetate—petrol 40/60 (1:1) followed by removal of solvent in vacuo andthorough drying gave the product as a yellow oil. (Yield 8.0 g, 94%)

Ir νmax (thin film): 2930, 2860, 1660 (s), 1530, 1470, 1450, 142, 1350,1280, 1230, 1195, 1115 (s), 995, 930, 755 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.70 (m, 8H), 3.90 (m, 4H), 4.0 (m, 4H), 4.25 (s, 4H),5.10-5.25 (m, 8H), 5.75-5.90 (m, 4H).

Monomer from step 1 above (1.0 g, 0.00263 mol) and 5 mol % Irgacure 184(27 mg, 0.00013 mol) were dissolved in dry dichloromethane (3 cm³ andthe solution spread over an 18×25 cm glass plate. The solvent wasallowed to evaporate to leave a thin clear film. The film was thenirradiated with a Philips UVA sunlamp (75 w) for approximately 5 minutesto form a hard polymeric cross-linked coating. The coating was removedand washed in dry dichloromethane and then thoroughly dried (Yield 0.73g, 73%)

Ir νmax (KCl disc): 2920, 2860, 1640 (s), 1530, 1450, 1240, 1115 (s),730 cm⁻¹.

EXAMPLE 8

3,6,9-Trioxaundecandioic acid (2.64 g, 0.012 mol), 1,1-diallylethanol(3.0 g, 0.023 mol), 1,3-dicyclohexylcarbodiimide (5.16 g, 0.025 mol) and4-dimethylaminopyridine (150 mg) were dissolved in dry dichloromethane(100 cm³) and the solution stirred for 18 h at room temperature.1,3-Dicyclohexylurea was removed by filtration and the solvent removedin vacuo to leave a yellow oil. Column chromatography using silica geland ethyl acetate gave, after removal of solvent in vacuo, a clear oil,4.9 g, 94%.

¹HNMR (CDCl₃) δ: 1.45 (s, 8H), 2.50-2.70 (m, A:B, 8H), 3.70 (s, 6H),4.05 (s, 4H), 5.05-5.15 (m, 8H), 5.70-5.90 (m, 4H).

Ir νmax (thin film): 2920, 2870, 1750, 1450, 1380, 1210, 1150, 1120,740, 700 cm⁻¹.

The monomer from Step 1 above (1.0 g, 0.0023 mol) and Irgacure 184 (5mol %; 23.5 mg, 0.00012 mol) were dissolved in dry dichloromethane (3cm³) and the solution spread over a 18×25 cm glass plate. The solventwas allowed to evaporate to leave a thin clear film. The film was themirradiated with a Philips UVA sunlamp (75 w) to form a hard cross-linkedpolymer coating. The coating was removed and washed in drydichloromethane and then dried thoroughly. Yield 0.78 g, 78%.

Ir νmax (KCl disc): 2940, 2880, 1750, 1450, 1380, 1205, 1145, 1120,1030, 960 cm⁻¹.

EXAMPLE 9

The diacid shown above (2.5 g, 0.0114 mol), 1,5-hexadien-3-ol (1.34 g,0.024 mol), 1,3-dicyclohexylcarbodiimide (206.33) (5.16 g, 0.025 mol)and 4-dimethylaminopyridine (200 mg) were placed in dry dichloromethane(100 cm³) and the solution stirred for 18 hours at room temperature.1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to leave a yellow oil. Column chromatography using silica gelwith ethyl acetate gave a clear oil, 2.84 g, 66%.

¹HNMR (CDCl₃) δ: 1.20 (quin, 2H), 1.65 (m 4H), 2.40 (t, 4H), 3.60 (d,4H), 4.20 (s, 4H), 5.05-5.45 (m, 10H), 5.65-5.90 (m, 4H).

Ir νmax (thin film): 2920, 2860, 1750, 1700, 1510, 1430, 1240, 1200,1140, 1030, 990, 920, 760 cm⁻¹.

Monomer from step 1 above (0.7 g, 0.001894 mol) and Irgacure 184 (37.6mg, 0.0000184 mol) were dissolved in dry dichloromethane (3 cm³) and thesolution was spread on an 18×25 cm³ glass plate. The solvent was allowedto evaporate to leave a clear film. This was irradiated with a PhilipsUVA (75 w) sunlamp for 2 hours until the film hardened. The film wasremoved and placed in dry dichloromethane (50 cm³) and stirred for 1hour. The cross-linked polymer was removed by filtration and washed withdry dichloromethane (2×50 cm³) and dried thoroughly to leave a creamycoloured polymeric solid. Yield 0.35 g, 50%.

Ir νmax (KCl disc) 2940, 2860, 1750 (s), 1450, 1285, 1205, 1130, 1030cm⁻¹.

EXAMPLE 10

Polyethylene glycol 600 diacid (12.0 g, 0.020 mol), diallylamine (4.67g, 0.048 mol), 1,3-dicyclohexylcarbodiimide (10.6 g, 0.048 mol) and4-dimethylaminopyridine (600 mg) were placed in dichloromethane (100cm³) and the mixture stirred for 24 hours at room temperature. The1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to leave a yellow oil. Column chromatography (silica gel/ethylacetate) followed by removal of solvent in vacuo gave a pale yellow oil.13.90 g, 92%.

¹HNMR (CDCl₃) δ: 3.60 (m, 48H), 3.90 (d, 4H), 4.0 (d, 4H), 4.20 (s, 4H),5.15 (m, 8H), 5.75 (m, 4H).

Ir νmax (thin film): 3016, 2922, 1662 (s), 1470, 1353, 1219, 1114, 931,756, 666 cm⁻¹.

Monomer from Step 1 (1.0 g) and Irgacure (1.5 mg) were dissolved in drydichloromethane (3 cm³) and thoroughly mixed. The solution was spreadevenly on an 18×25 cm glass plate and the solvent allowed to evaporateto leave a thin film of monomer. The film was irradiated with thePhilips UVA (75 w) sunlamp for 30 minutes to form a soft, permeable towater, cross-linked polymer film.

Ir νmax (thin film): 3438, 2946, 2371, 1703, 1648 (s), 1544, 1510, 1457,1352, 1099 (vs), 953, 856, 727, 551 cm⁻¹.

EXAMPLE 11

Diallylamine (9.72 g, 0.1 mol), Sebacic acid (10.00 g, 0.0050 mol),1,3-dicyclohexylcarbodiimide (22.70 g. 0.11 mol) and4-dimethylaminopyridine (0.450 g) were stirred together in drydichloromethane (100 cm³) for 6 hours. The resultant1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to give a yellow oil. Column chromatography using ethylacetate—petrol 40/60 (1:1) followed by removal of solvent in vacuo andthorough drying gave the product as a yellow oil. 15.90 g, 90%.

Ir νmax (thin film): 2920, 2850, 1690 (w), 1640 (s), 1520, 1460, 1410,1220, 990, 920, 730 cm⁻¹.

¹HNMR (CDCl₃) δ: 1.10-1.45 (m, 6H), 1.50-2.00 (m, 6H), 2.40 (t, 4H),3.90 (d, 4H), 4.0 (d, 4H), 5.05-5.20 (m, 8H), 5.20-5.90 (m, 4H).

Monomer from Step 1 (1.00 g, 0.0028 mol) and Irgacure 184 (28.3 mg,0.000139 mol) were dissolved in dry dichloromethane (3 cm³) and thesolution spread over a 18×25 cm glass plate. The solvent was allowed toevaporate to leave a thin clear film. The film was then irradiated witha Philips UVA sunlamp (75 w) for approximately 5 minutes to form a hardpolymeric cross-linked coating. The coating was removed and washed indry dichloromethane and then thoroughly dried.

Yield 0.80 g, 80%. Ir νmax KCl disc): 2920, 2860, 1640, 1530, 1450, 1230(w), 1340 (w), 1230 (w), 1000 (w), 930 (w).

EXAMPLE 12

Eicosanedioic acid (5.0 g, 0.0146 mol), diallylamine (3.12 g, 0.032mol), 1,3-dicyclohexylcarbodiimide (6.60 g, 0.032 mol) and4-dimethylaminopyridine (200 mg) were dissolved indichloromethane/tetrahydrofuran mixture (1:1) (100 cm³) and the mixturestirred at room temperature for 72 hours. 1,3-Dicyclohexylurea wasremoved by filtration and the solvent removed in vacuo to leave a yellowoil. Column chromatography using silica gel/ethyl acetate followed byremoval of solvent in vacuo and thorough drying gave a pale yellow oil.6.35 g, 87%.

¹HNMR (CDCl₃) δ: 1.20 (s, br, 28H), 1.60 (m, 4H), 1.80 (m, 4H), 3.90 (d,4H), 4.0 (d, 4H), 5.10 (m, BH), 5.75 (m, 4H).

Ir νmax (thin film): 3006, 2927, 2854, 1643, 1530, 1466, 1415, 1217,1084, 992,. 925, 893, 756, 666 cm⁻¹.

Monomer from Step 1 (0.25 g) and Irgacure 184 (5 mg) were dissolved indry dichloromethane (1.0 cm³) and the solution was heated (water bath)to ensure even distribution of photoinitiator. The solution was spreadevenly on a 4×2″ piece of aluminium foil and the solvent was allowed toevaporate off to leave a thin film of monomer/photoinitiator. This wasirradiated with a Philips UVA (75 w) sunlamp for 30 minutes until a hardcross-linked polymer was formed. To test for hydrophobicity, thefoil+polymer was subjected to running water for 30 minutes. After thistime the polymer laminate was not adversely affected, i.e. no loss ofadhesion to the foil.

Ir νmax (KCl disc): 2924, 2851, 1648, 1534, 1452, 1227, 721 cm⁻¹.

EXAMPLE 13

Diallylamine (12.90 g, 0.132 mol), 1,2-dibromoethane (12.40 g, 0.066mol) and potassium carbonate (18.80 g, 0.132 mol) were refluxed inethanol (100 cm³) for 24 hours. Solids were removed by filtration andsolvents removed in vacuo to leave a yellow oil. The oil was purified bycolumn chromatography (silica gel/ethyl acetate) to leave a pale yellowoil. 13.40, 92%.

¹HNMR (CDCl₃) δ: 2.55 (s, 4H), 3.10 (d, 8H), 5.10 (m, 8H), 5.80 (m, 4H).

Ir νmax (thin film): 3082, 3012, 2983, 2927, 2806, 1645, 1447, 1420,1355, 1262, 1109, 997, 919, 559 cm⁻¹.

Monomer from Step 1 (5.0 g) was treated with an aqueous methanolicsolution of hexafluorophosphonic acid 60% solution in H₂O (3.0 m) topH1. The PF₆ ⁻ salt was extracted using dichloromethane (2×100 cm³) andthe combined extracts were dried over MgSO₄. Removal of solvent left ayellow oil. 8.0 g, 96%.

¹HNMR (CDCl₃) δ: 3.60 (d, 2H), 3.75 (d, 2H), 3.80 (s, 8H), 5.55 (m, 8H),5.90 (m, 4H), 9.80 (s, br, 2H).

Ir νmax (thin film): 3428, 2986, 2634, 1460, 1426, 1294, 1246, 1142,1053, 977, 953, 842, 740 cm⁻¹.

The product may then be polymerised, for example as described in Example1 Step 3 above.

EXAMPLE 14

Diallylamine (1.41 g, 0.0145 mol), perfluoro-1,10-decanedicarboxylicacid (2.5 g, 0.0073 mol), 1,3-dicyclohexylcarbodiimide (3.20 g, 0.0155mol) and 4-dimethylaminopyridine (0.5 g) were stirred together in drydichloromethane (60 cm³) for 6 hours. The solvent was removed in vacuoto leave a white solid which was purified using column chromatography(ethyl acetate-petrol 40/60 1:1) and dried thoroughly to give 2.96 g,79% of clear oil.

¹HNMR (CDCl₃) δ: 3.90 (d, 4H), 4.00 (d, 4H), 5.10-5.25 (m, 8H),5.70-5.81 (m, 4H).

Ir νmax (thin film): 2933, 2857, 1692, 1645.5, 1611.4, 1576, 1454, 1419,1377, 1350, 1219, 1151, 1081, 992, 932, 892, 735, 657, 556.

Monomer from Step 1 (1.0 g, 0.0019 mol) was dissolved in drydichloromethane (3 cm³) and Irgacure 184 (20 mg, 0.000095 mol) and theresultant solution spread evenly over an 18×25 cm glass plate. Thesolvent was allowed to evaporate off to leave a clear liquid layer ofmonomer/photoinitiator. The plate was placed under a Philips UVA (75 w)sunlamp for approximately 15 minutes. The resultant clear film wasremoved (powdery) and dried after stirring for 30 minutes in drydichloromethane (100 cm³) to leave 0.79 g, 79% of white powder.

Ir νmax (thin film): 2936, 2859, 1691, 1624, 1576, 1455, 1372, 1218,1151, 1079, 892, 729, 654, 555 cm⁻¹.

EXAMPLE 15

Sebacic acid (2.0 g, 0.0099 mol), 1,4-pentan-3-ol (1.7 g, 0.02 mol),1,3-dicyclohexylcarbodiimide (4.52 g, 0.022 mol) and4-dimethylaminopyridine (200 g) in dry dichloromethane (60 cm³) werestirred together for 18 hours. The 1,3-dicyclohexylurea was removed byfiltration and solvent removed to leave clear oil. This was dissolved in40/60 petrol (100 cm³) and washed in water then dried over MgSO₄.Removal of solvent left a clear, colourless oil which tlc(dichloromethane) (developing in iodine) showed as a single spot. Theoil was thoroughly dried it vacuo to leave 2.49 g, 75% of clear oil.

¹HNMR (CDCl₃) δ: 1.30 (s, 8H), 1.60 (t, 4H), 2.35 (t, 4H), 5.15-5.35 (m,8H), 5.65-5.95 (m, 6H).

Ir νmax (thin film): 2920, 2860, 1730, 1640, 1510, 1460, 1410, 1365,1240, 1165, 1095, 985, 930 cm⁻¹.

Monomer from Step 1 (1.0 g, 0.003 mol) and Irgacure 184 (31 mg, 0.00015mol) were dissolved in dry dichloromethane (2 ml) and the solution wasspread evenly on an 18×25 cm plate glass sheet. The solvent was allowedto dry in air then the remaining polymer/photoinitiator film wasirradiated beneath a Philips UVA (75 w) sunlamp for 2 hours. Theresultant cross-lnked polymer was scraped (scalpel) from the plate andsuspended in dry dichloromethane (20 ml) and the suspension was stirredfor approximately 15 minutes. The polymer was recovered by filtrationand the retained solid washed with dry dichloromethane (2×10 cm³) andthen dried thoroughly to leave 0.85 of clear film polymeric material.

Yield 0.85 g, 85%.

Ir νmax (thin film): 2920, 2860, 1725, 1520, 1450, 1365, 1240, 1170,1090, 985 cm⁻¹.

EXAMPLE 16

Diallylamine (12.70 g, 0.134 mol), 1,12-dibromododecane (20.0 g, 0.061mol) and potassium carbonate(18.50 g, 0.134 mol) in ethanol (100 cm³)were refluxed together for 18 hours. The solids were removed byfiltration and the solvent removed in vacuo to leave a yellow oil. Theoil was passed through a silica gel column using ethyl acetate as theeluent. Removal of solvent in vacuo gave a pale yellow oil which wasthoroughly dried. Yield 17.4 g, 79%.

¹HNMR (CDCl³) δ: 1.20 (m, 16H), 1.45 (t, 4H), 2.40 (t, 4H), 3.10 (d,8H), 5.05-5.15 (m, 8H), 5.80 (m, 4H).

Ir νmax (thin film): 3080, 3020, 2920, 2860, 2800, 1645, 1470, 1420,1355, 1260, 1155, 1115, 1090, 1000, 920, 725 cm⁻¹.

The diamine from step 1 (10.00 g, 0.028 mol) and methyl iodide (8.52 g,0.060 mol) in a mixture of tetrahydrofuran (100 cm³) and dichloromethane(20 cm³) were stirred together. After 0.5 hours the solution began tobecome turbid and the turbidity increased as time progressed. Thesolvent was removed in vacuo and the white solid residue was suspendedin 40/60 petrol (100 cm³) and stirred for 1 hour. Filtration andthorough drying in vacuo gave 17.40 g, 97% of white, soft solid.

¹HNMR (CD₂Cl₂) δ: 1.15-1.40 (m, 16H), 1.80 (s, br, 4H), 3.20 (s, 6H),3.30-3.45 (m, 4H), 4.15 (d, 8H), 5.65-5.90 (m, 8H), 5.95-6.15 (m, 4H).

Ir νmax (thin film): 2920, 2860, 1690, 1640, 1470, 1370, 1300, 1250,1000, 945 cm⁻¹.

This material could be polymerised as described in previous examples.

EXAMPLE 17

Diallylamine (8.80 g, 0.0090 mol), 3,6-dioxaoctandioic acid (8.00 g,0.0448 mol) were mixed together as shown in Example 15 Step 1. Themixture was stirred in dichloromethane for 24 hours. The crude productwas recovered and purified via silica gel/ethyl acetate to leave a clearoil. Yield 13.43 g, 89%.

¹HNMR (CDCl₃) δ: 3.70 (s, 4H), 3.80 (d, 4H), 3.95 (d, 4H), 4.20 (s, 4H),5.20 (m, 8H), 5.60 (m, 4H).

Ir νmax (thin film): 3080, 2940, 2860, 1650, 1530, 1470, 1420, 1350,1280, 1235, 1120, 995, 930, 860, 815 cm⁻¹.

Irgacure 184 (5 mg) as placed in Monomer from Step 1 (0.2 g) and heatedto form a clear solution. It was then stirred to ensure complete mixingof photoinitiator then placed on a 1.5 in² piece of copper (ex DRA) andspread evenly using 100 μm K bar. It was then irradiated for 1 hourbeneath a Philips UVA sunlamp and allowed to stand for 24 hours.

Ir νmax (thin film): 2940, 2860, 1640 (strong), 1460, 1345, 1125, 730cm⁻¹.

EXAMPLE 18

Meso-butan-1,2,3,4-tetracarboxylic acid (20.0 g, 0.0428 mol),diallylamine (39.0 g, 0.20 mol), 1,3-dicyclohexylcarbodiimide(82.50 g,0.20 mol) and 4-dimethylaminopyridine (2.0 mg) were dissolved indichloromethane/tetrahydrofuran (1:1) mixture (200 cm³) and the mixturewas stirred at room temperature for 120 hours. 1,3-dicyclohexylurea wasremoved by filtration and the solvent removed in vacuo to leave a yellowoil. Column chromatography (silica gel/ethyl acetate) followed byremoval of solvent in vacuo gave a heavy pale yellow oil whichsolidified on standing. 42.3 g, 89%.

¹HNMR (CDCl₃) δ: 2.90 (m, 4H), 3.50 (m, 2H), 3.80 (m, 16H), 5.20 (m,16H), 5.70 (m, 8H).

Ir νmax (thin film): 3323, 3086, 2935, 2861, 1650, 1545, 1416, 1363,1228, 1135, 994, 925, 556 cm⁻¹.

Monomer from Step 1 (1.0 g) was dissolved in dry dichloromethane (3cm³). The Irgacure 184 (10 mg) was added to the solution, heated andmixed to ensure homogenicity. It was then spread evenly on an 18×25 cmglass plate and the solvent allowed to evaporate off to leave a thin,clear film. This was irradiated with a Philips UVA sunlamp for 30minutes to form a hard cross-linked polymer film. This was removed(scalpel), washed in dichloromethane and dried. Yield 0.64 g, 64%.

Ir νmax (thin film): 3424, 2936, 2374, 2346, 1705, 1644 (s), 1524, 1436(s), 1222, 1138, 992, 924, 561 cm⁻¹.

EXAMPLE 19

Polyethylene glycol 600 diacid (6.0 g, 0.010 mol), 1,4-pentadiene-3-ol(2.0 g, 0.024 mol), 1,3-Dicyclohexylcarbodiimide (206.33) (4.95 g, 0.024mol) and 4-dimethylaminopyridine (300 mg) were stirred together in drydichloromethane (50 ml) for 72 h. The resultant 1,3-Dicyclohexyl-ureawas removed by filtration and removal of solvent left a clear oil.Column chromatography using silica gel and dichloromethane—40/60 petrol(1:1) followed by dichloromethane-methanol (1:3) gave, after removal ofsolvent, a colourless, clear oil. 6.73 g, 85%.

¹HNMR (CDCl₃) δ: 3.55-3.80 (m, 48H), 4.15 (s, 4H), 5.25-5.50 (m, 10H),5.75-5.95 (m, 4H).

Ir νmax (thin film): 2860, 1745, 1635, 1450, 1345, 1250, 1195, 1140,1115, 990, 940, 750 cm⁻¹.

Monomer from Step 1 (1.6og, 0.0021 mol) and Irgacure 184 (21 mg,0.000105 mol) were dissolved in dry dichloromethane (3 cm³) and thesolution was spread over a 18×25 cm glass plate. The solvent was allowedto evaporate to leave a thin, clear film. The film was then irradiatedwith a Philips UVA sunlamp (75 w) to form a hard cross-linked polymercoating. The coating was removed and, washed in dry dichloromethane anddried thoroughly.

Yield 1.10 g, 67%.

Ir νmax (KCl disc): 2920, 2860, 1745, 1680, 1640, 1450, 1345, 1280,1250, 1200, 1140, 1110, 950, 850 cm⁻¹.

EXAMPLE 20

The Monomer of Example 12 Step l (0.5 g) and the monomer of Example 11Step 1, were dissolved with the Irgacure 184 (20 mg) in dichloromethane(5 cm³) and the solution was spread evenly on an 18×25 cm glass plate.The solvent was evaporated off and the residual film irradiated with thePhilips UVA (75 w) sunlamp for 1 hour. The resultant cross-linkedcopolymeric film was removed in strips (scalpel) and washed indichloromethane, then thoroughly dried. The resultant film was soft,stretchy but of low tensile strength.

Ir νmax (thin film): 3431, 2931, 2858, 1649 (s), 1453, 720 cm⁻¹.

EXAMPLE 21

The monomer of Example 11 Step 2 (0.5 g) and monomer B above (0.5 g)(prepared by analgous methods to those described above) were dissolvedin dry dichloromethane (5 cm³). The Irgacure 184 (20 mg) was added andthe mixture warmed (water bath) until the photoinitiator had dissolved.The solution was spread evenly on an 18×25 cm glass plate and thesolvent allowed to evaporate. The two monomers phase separated to givean even ‘pimpled’ effect. Attempts to mix the two monomers usingdichloromethane and mechanical mixing resulted, after evaporation ofsolvent, in the same pimpled effect. The monomers were irradiated withthe Philips UVA (75 w) sunlamp for 1 hour to form a phase-separatedcross-linked solid polymeric ‘pimpled’ film but unstable due to thediscontinuity of polymerisation at each phase boundary.

Ir νmax (thin film): 3421 (s), 2939 (s9), 1642 (s), 1456, 1167, 577cm⁻¹.

EXAMPLE 22

The monomer of Example 11 step 1 (0.5 g) and the monomer of Example 3Step 2 (0.5 g), were dissolved with the Irgacure 184 (20 mg) indichloromethane (5 cm³) and the solution was evenly spread on an 18×25cm glass plate. The solvent was evaporated off to leave a residual clearfilm which was irradiated with the Philips UVA (75 w) sunlamp for 1hour. The resultant cross-linked copolymer was removed in strips(scalpel) and washed in dichloromethane (50 cm³) then thoroughly dried.

Ir νmax (thin film): 3448 (s), 2931, 2855, 1629 (s), 1534, 5 1452, 1230,731 cm⁻¹.

EXAMPLE 23

Other polymerisable monomers were produced as follows:

EXAMPLE 23a

The monomer illustrated (5.0 g) above was treated with a 50% aqueoussolution of fluoroboric acid to pH 1.0 (universal indicator paper). Theorganic phase was extracted using dichloromethane (2×75 cm³) and thendried over MgSO₄Removal of solvent in vacuo gave a heavy pale yellowoil. 7.40 g, 97%.

¹HNMR (CDCl₃) δ: 1.20 (s, br, 12H), 1.65 (s, br, 4H), 3.05 (quin, 4H),3.75 (t, 8H), 5.55 (m, 8H), 5.90 (m,4H), 7.15 (s, br, 2H).

Ir νmax (thin film): 3410 (br), 2930, 2857, 2649, 1707, 1646, 1460,1428, 1056.8 (very strong), 952, 763 cm⁻¹.

EXAMPLE 23b

Using the procedure described in Example 23a, sebacic acid 10.06 g,0.050 mol), 1,5-Hexadiene-3-ol (9.80 g, 0.1 mol),1,3-dicyclohexylcarbodiimide (22.70 g, 0.11 mol) and4-dimethylaminopyridine (450 mg) were mixed together to give the desiredproduct.

Yield: 15.6 g, 87%; ¹HNMR (CDCl₃) δ: 1.30 (s, 10H), 1.60 (t, 8H), 2.35(s, 2H), 5.05-5.45 (m, 10H), 5.65-5.90 (m, 4H).

Ir νmax (thin film): 2920, 2860, 1730, 1640, 1510, 1460, 1410, 1365,1235, 1160, 1095 cm⁻¹.

EXAMPLE 24

Diallylamine (10.09, 0.103 mol), allyl bromide (25.41 g, 0.21 mol) andpotassium carbonate (20 g) were refluxed in ethanol. Solids were removedby filtration and the solvents were removed in vacuo to leave a yellowoil.

This compound could be used as a u.v curable adhesive.

EXAMPLE 25

1-Bromooctane (15.0 g, 0.078 mol), diallylamine (8.26 g, 0.085 mol) andpotassium carbonate (11.75 g, 0.085 mol) were refluxed in ethanol (100cm³) for 18 hours. Solids were removed by filtration and the solventswere removed in vacuo to leave a yellow oil. Column chromatography(silica gel/dichloromethane) followed by removal of solvent in vacuo andthorough drying gave 12.9 g, 79% of light yellow oil.

¹HNMR (CDCl₃) δ: 0.85 (t, 3H), 1.80 (s, br, 10H), 1.45 (s, br, 2H), 2.40(5, 2H), 3.15 (d, 4H), 5.10 (m, 4H), 5.85 (m, 2H).

Ir νmax (thin film): 3082, 2932, 2860, 2806, 2355 (w), 1751 (w), 1709(w), 1644 (m), 1463, 1419, 1379, 1262, 1083, 996, 919, 613 cm⁻¹.

EXAMPLE 26

Benzoic acid (20.0 g, 0.164 mol) was placed in thionyl chloride (23.80g, 0.20 mol) and the mixture heated to approximately 80° C. withstirring for 3 hours. Excess thionyl chloride was removed in vacuo andthe residue cooled to approximately −5° C. in a salt/ice bath.Diallylamine (19.50 g, 0.20 mol) in dry dichloromethane (20 cm³) wasadded dropwise with much evolution of HCl gas. After complete addition,the resultant brown solution was allowed to rise to room temperature andleft stirring for one hour. It was then washed with 3N HCl (150 cm³),saturated K₂CO₃ solution (150 cm³) and brine (150 cm³), then finallydried over MgSO₄. Removal of solvent gave a brown oil which was passedthrough a silica gel column using ethyl acetate as the eluent. Removalof solvent in vacuo gave a yellow oil. 27.10 g, 82%.

¹HNMR (CDCl₃) δ: 3.90 (s, br, 2H), 4.10 (s, br, 2H), 5.20 (m, 4H), 5.70(s, br, 1H), 5.85 (s, br, 1H), 7.40 (m, 5H).

Ir νmax (thin film): 3087, 1640, 1498, 1456, 1413, 1262, 1120, 991, 928,788, 703 cm⁻¹.

EXAMPLE 27

Heptanoyl chloride (25.0 g, 0.168 mol) was placed in dry dichloromethane(100 cm³) and the solution cooled to −5° C. in a salt-ice bath.Diallylamine (17.5 g, 0.18 mol) in dry dichloromethane (25 cm³) wasadded dropwise with much evolution of HCl gas. The resultant solutionwas allowed to rise to room temperature then poured into 3N HCl (300cm³) and stirred vigorously for ten minutes. The organic layer wasremoved by separation and to the aqueous layer was added ammoniumchloride. This was then re-extracted with dichloromethane (2×100 cm³)and the three organic extracts combined and dried over MgSO₄. Removal ofsolvent in vacuo left a brown oil (one spot on tlc—silica gel/ethylacetate) which was passed through a silica gel column using ethylacetate as the eluent. Removal of solvent in vacuo gave a yellow oil.32.0 g, 91%.

¹HNMR (CDCl₃) δ: 0.90 (t, 3H), 1.35 (m, 6H), 1.65 (quin, 2H), 2.35 (t,2H), 3.90 (m, 2H), 4.0 (m, 2H), 5.15 (m, 4H), 5.75 (m, 2H).

Ir νmax (thin film): 2933, 2861, 2338, 1722, 1655, 1563, 1466, 1415,1227, 1114, 995, 923 cm⁻¹.

EXAMPLE 28

Oxalyl Chloride (25.0 g, 0,197 mol) was placed in dry dichloromethane(150 cm³) and cooled to −5° C. and stirred. The diallylamine (48.6 g,0.50 mol) in dry dichloromethane (50 cm³) was slowly added dropwise(much HCl evolved!) keeping temperature below 20° C. After addition thesolution was stirred at room temperature for thirty minutes and thenwashed with 3N HCl (100 cm³), saturated K₂CO₃ (100 cm³), brine (100cm³), and finally dried over MgSO₄. Removal of solvent left a brown oil(one spot by tlc, silica gel/EtOAc). The oil was passed through a silicagel column using ethyl acetate as the eluent. Removal of solvent left ayellow oil. 42.50 g, 87%.

¹HNMR (CDCl₃) δ: 3.85 (m, 4H), 4.0 (m, 4H), 5.15 (m, 8H), 5.80 (m, 4H).

Ir νmax (thin film): 308.8, 2991, 1654, 1488, 1413, 1285, 1215, 1128,996, 930, 783, 720 cm⁻¹.

EXAMPLE 29

Acryloyl chloride (25.0 g, 0.28 mol) was placed in dry dichloromethane(150 cm³) and cooled to −5° C. in a salt/ice bath and stirred. Thediallylamine (29.15 g, 0.30 mol) in dry dichloromethane (50 cm³)was-added dropwise over ˜1 h* and the resultant solution allowed to riseto room temperature and stirred for 30 minutes. The solution was treatedwith 3N HCl (100 cm³) saturated K₂CO₃ solution (100 cm³) and brine (100cm³) then dried over MgSO₄. Removal of solvent gave a brown oil. The oilwas passed through a silica gel column using ethyl acetate as eluent.Removal of solvent gave a yellow oil 37.1 g 89%.

* evolution of HCl

Ir νmax (thin film).: 2988, (1726), 1657, 1618, 1470, 1443, 1226, 1196,1077, 989, 926, 795 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.95, (d, 2H), 4.05 (d, 2H), 5.15 (m, 4H), 5.65 (m,1H), 5.75 (m, 2H), 6.90 (m, 2H).

EXAMPLE 30

Malonic acid (16.23 g, 0.156 mol), diallylamine (31.1 g, 0.320 mol) and1,3-dicyclohexylcarbodiimide (66.0 g, 0.320 mol) were placed in drydichloromethane and the mixture stirred for 18 hours at roomtemperature. The copious quantity of 1,3-dicyclohexyl-urea was removedby filtration (Whatman No. 1 filter paper) and the organic filtratewashed with 3N HCl (150 cm³), then saturated potassium carbonatefollowed by water (150 cm³) The solution was dried over MgSO₄ andremoval of solvent gave a brown oil. The oil was passed through a silicagel column using ethyl acetate as eluent. Further decoloration wasachieved using charcoal and dichloromethane/40/60 petrol (1:1) assolvent. Filtration and removal of solvent in vacuo gave a yellow/brownoil. 33.70 g, 87%.

¹HNMR (CDCl₃) δ: 3.55 (s, 2H), 4.04 (d, 8H), 5.15 (m, 8H), 5.80 (m, 4H).

Ir νmax (thin film): 2987, 2934, 1652, 1414, 1310, 1223, 1193, 1136,996, 922, 852, 700, 556 cm⁻¹.

EXAMPLE 31

Succinic anhydride (50.0 g, 0.5 mol) was placed in a dry dichloromethane(400 cm³) and stirred and cooled to −5° C. in a salt/ice bath.Diallylamine (48.6 g, 0.5 mol) in dry dichloromethane (100 cm³) wasadded dropwise over 1 hour keeping the temperature at >20° C. Asaddition proceeded, the succinic anhydride, suspended in dichloromethanebecame less evident until all had reacted to form a pale yellowsolution. The solution was washed in 3N HCl solution (200 cm³),saturated K₂CO₂ (200 cm³) then water (200 cm³) and finally dried overMgSO₄. Removal of solvent left a light yellow oil (of one spot purity ont.l.c.). 95.46 g, 96%.

¹HNMR (CDCl₃) δ: 2.65 (m, 4H), 3.95 (d, 2H), 4.05 (d, 2H), 5.15 (m, 4H),5.75 (m, 2H).

Ir νmax (thin film): 3088 (br), 1737, 1650, 1480, 1418, 1233, 1176, 995,928, 829, 558 cm⁻¹.

EXAMPLE 32

Diallylamine (17.0 g, 0.185 mol) and 1,3-dicyclohexylcarbodiimide (36.12g, 0.175 mol) were dissolved in dry dichloromethane (150 cm³) and thesolution cooled to 0° C. Trifluoroacetic acid (20.0 g, 0.175 mol) in drydichloromethane (50 cm³) was added dropwise over 1 hour and the wholewas left stirring at room temperature for 72 hours. The1,3-dicyclohexylurea was removed by filtration and the solvent removedin vacuo to leave a yellow oil. Column chromatography (silicagel—dichloromethane) followed by removal of solvent in vacuo gave a paleyellow oil which crystallised slowly on standing. 26.67 g, 79.0%.

¹HNMR (CDCl₃) δ: 4.0 (d, 4H), 5.20 (m, 4H), 5.75 (m, 2H).

Ir νmax (thin film): 2935, 2866, 1698, 1559, 1454, 1348, 1305, 1160,1050, 994, 926, 895 cm⁻¹.

EXAMPLE 33

Cyanoacetic acid (25.0 g, 0.294 mol) in dry dichloromethane (100 cm³)was added dropwise to a solution of diallylamine (29.0 g, 0.30 mol) and1,3-dicyclohexylcarbodiimide (64.0 g, 0.31 mol) in dry dichloromethane(250 cm³). The mixture was left stirring for 15 hours at roomtemperature. The 1,3-dicyclohexylurea was removed by filtration and thesolvent removed to leave a brown oil. Column chromatography (silicagel—dichloromethane) followed by removal of solvent in vacuo left alight yellow oil. 40.50 g, 84%.

¹HNMR (CDCl₃) δ: 3.75 (s, 2H), 4.0 (d, 2H), 4.10 (d, 2H), 5.40 (m, 4H),5.90 (m, 2H).

Ir νmax (thin film): 3091, 2931, 2261, 1674, 1448, 1316, 1229, 1192,1139, 996, 931, 820 cm⁻¹.

EXAMPLE 34

Acryloyl Chloride (16.5 g, 0.180 mol) was dissolved in drydichloromethane (50 cm³) and the solution was cooled to −5° C. in asalt/ice bath and stirred. The allylamine (5.0 g, 0.087 mol) in drydichloromethane (25 cm³) was added dropwise over 30 minutes and theresultant solution was allowed to rise to room temperature and stirredfor a further 30 minutes. The solution was treated with 3M HCl (50 cm³),saturated K₂CO₃ solution (50 cm³) and brine (50 cm³) then dried overMgSO₄. Removal of solvent gave a yellow oil. The oil was passed througha silica gel column using ethyl acetate as the eluent. Removal ofsolvent gave a yellow oil. 8.90 g, 92%.

¹HNMR (CDCl₃) δ: 3.95 (t, 2h), 5.15 (m, 2h), 5.60 (m, 1h), 5.85 (m, 1h),6.20 (m, 2h), 6.70 (s, br, 1H).

Ir νmax (thin film): 3289, 3084, 1664, 1628, 1549, 1412, 1246, 1070,989, 922, 808 cm⁻¹.

EXAMPLE 35

Methane sulphonyl chloride (10.0 g, 0.087 mol), diallyamine (8.75 g,0.090 mol) and potassium carbonate (10 g) were placed in sieve-driedbutanone (100 cm³) and the mixture was refluxed with stirring for 3hours. Thin layer chromatography (ethyl acetate) showed a product spotat ˜Rf 0.5 with no evidence of diallyamine remaining. The reactionmixture was filtered (Whatman No. 1 filter paper) and the solvent wasremoved in vacuo to leave a brown oil. The oil was purified using columnchromatography using silica gel and ethyl acetate-petrol 40/60 (1:1) aseluent. Removal of solvent in vacuo gave the product as a yellow oil(12.30 g, 80%)

Ir νmax (thin film): 3089, 2990, 1331 (s), 1150, 1046, 996, 934,793, 733cm⁻¹;

¹HNMR (CDCl₃) δ: 2.90 (s,3H), 3.85 (d, 4H)m 5.2 (m,4H), 5.80 (m,2H).

The compounds of each of Examples 24 -35 above had the properties of au.v. curable adhesive.

EXAMPLE 36

Amide A (5.0 g, 0.023 mol), diethanolamine (2.40 g, 0.023 mol) andpotassium carbonate (3.45 g (0.025 mol) in ethanol (50 cm3) were stirredtogether at reflux for 15 h. The solids were removed by filtration(Whatman No. 1) and the solvent removed in vacuo to leave a brown oil.Column chromatography (silica gel/ethyl acetate) followed by removal ofsolvent in vacuo and thorough drying left 4.8 g, 87% as a yellow oil.

Ir νmax (thin film): 3650-3100, 2937, 1646 (S), 1419, 1354, 1229, 1131,995, 927, 754 cm⁻¹.

¹HNMR (CDCl₃) δ: 2.80 (t, 2H), 3.40 (t, 2H), 3.50 (s, 2H), 3.90 (d, 2H),4.0 (d, 2H), 5.15 (m, 4H), 5.85 (m, 2H).

EXAMPLE 37

Diethanolamine (10.0 g, 0.095 mol), allyl bromide (24.2 g, 0.20 mol) andpotassium carbonate (34.5 g, 0.25 mol) were placed in ethanol (150 cm³)and the mixture was warmed to 65-70° C. with stirring and kept at thistemperature for 15 h. Solids were removed by filtration and the solventremoved in vacuo to leave a yellow oil, 21.7 g, 86%.

Ir νmax (thin film): 3600-3100 (s), 2980, 1647, 1457, 1366, 1090, 955,754 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.62 (s, 2H), 3.78 (d, 2H), 3.98 (s, 2H), 4.10 (m, 4H),4.24 (m, 4H), 5.24 (m, 4H), 6.10 (m, 2H).

EXAMPLE 38

Glutaric anhydride (30.0 g, 0.26 mol) was placed in dry dichloromethane(150 cm³) and the mixture cooled (salt/ice bath) and stirred.Diallylamine (27.20 g, 0.28 mol) in dry dichloromethane (50 cm³) wasadded dropwise to form a clear yellow solution which was stirred for afurther 30 min. It was then washed with 3N HCl (200 cm3) then brine (200cm3) and dried over MgSO4. Removal of solvent left a yellow oil, 53.7 g,98%.

Ir νmax (thin film): 2500-3600, 1715, 1605, 1640, 1480, 1410, 1215, 995,920 cm⁻¹.

¹HNMR (CDCl₃) δ: 1.95 (quin, 2H), 2.45 (m, 4H), 3.90 (d, 2H), 3.98 (d,2H), 5.15 (m, 4H), 5.75 (m, 2H), 11.10 (s, 1H).

EXAMPLE 39

Bromoacetyl bromide (30.0 g, 0.15 mol) was dissolved in drydichloromethane (200 cm³) and the solution stirred at room temperature.Diallylamine (14.50 g, 0.15 mol) in dry dichloromethane (50 cm³) wasadded dropwise with much evolution of HCl gas, after complete additionthe solvent was removed in vacuo to give a brown oil. Columnchromatography (silica gel/ethyl acetate) followed by removal of solventgave a yellow oil, 31.4 g, 97%.

Ir νmax (thin film): 3513, 3087, 2989, 2927, 1657, 1449, 1343, 1257,1212, 1108, 994, 922, 728, 689, 618, 555 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.85 (s, 2H), 3.95 (m, 4H), 5.20 (m, 4H), 5.80 (m, 2H).

EXAMPLE 40

Hexafluoroglutaric anhydride (5.0 g, 0.0225 mol) was dissolved in drydichloromethane (100 cm³) and the solution was cooled to ˜−5° C. in asalt/ice bath. Diallylamine (2.20 g, 0.022 mol) in dry dichloromethane(20 cm³) was added dropwise over 15 minutes and the mixture stirred for30 minutes at room temperature. Aqueous HCl (6N) (100 cm3) was added andthe mixture stirred for 10 minutes. The organic layer was separated anddried over MgSO4. Removal of solvent gave a brown oil, 5.50 g, 77%.

Ir νmax (thin film): 3095, 3650-2500, 1786, 1678 (s), 1422, 1244, 1164,1052, 993 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.67 (˜1H, 4.0 (d, 2H), 4.05 (d, 2H), 5.25 (m, 4H),5.76 (m, 2H), 12.0 (s, 1H), 5.43 (s˜½H), 5.46 (d, ˜½H)

EXAMPLE 41

Amide A (5.0 g, 0.0254 mol) and triethanolamine (3.78, 0.0254 mol) weredissolved in dry dichloromethane (100 cm³ ) and stirred at roomtemperature for 1 hr. The solvent was removed in vacuo to leave a paleyellow oil (8.78 g, 100%) which was not purified since both of thestarting materials were 98-100% pure.

¹HNMR (CDCl₃) δ: 2.55 (m, 2H), 2.60 (m, 2H), 2.98 (t, 6H), 3.75 (t, 6H),3.95 (m, 4H), 5.15 (m, 1H), 5.76 (m, 2H), 6.32 (s, br, 4H).

Ir νmax (thin film): 3363 (s), 3156, 2936, 1639 (s), 1579 (s), 1409,1249, 1080, 1032, 1003, 918, 563 cm⁻¹.

EXAMPLE 42

Amide A (5.0 g, 0.0254 mol) and tris(hydroxymethyl)aminoethane (3.08 g,0.0254 mol) were placed together in dry dichloromethane (100 cm3) andthe combination stirred for 1 h at room temperature. The solvent wasremoved in vacuo to leave a pale yellow oil which was not furtherpurified since both starting materials were 98-100% pure. Yield 8.08 g,100%.

¹HNMR (CDCl₃) δ: 2.40 (s, br, 2H), 2.60 (s, br, 2H), 3.75 (s, br, 8H),3.95 (s, br, 2H), 5.15 (m, 4H), 5.70 (m, 2H), 6.85 (s, br, 6H, —OH₁+NH).

Ir νmax (thin film): 3392, 1561, 1463, 1407, 1221, 1190, 1063, 933, 565cm⁻¹.

EXAMPLE 43

Glutaric anhydride (3.68 g, 0.032 mol) was placed in dry dichloromethane(100 cm³) but did not dissolve. Dipropargylamine (3.00 g, 0.032 mol) indry dichloromethane (25 m³) was added slowly dropwise with a rise intemperature due to an exothermic reaction. As addition of thedipropargylamine proceeded, the glutaric anhydride became less evidentuntil a clear yellow reaction mixture was formed. This was left stirringfor a further 1 h. The solution was washed in (i) dil (1N)(50 ml) HClsolution, (ii) NaHCO₃ solution (1N) (50 ml), water (50 ml), then driedover MgSO₄ to leave an orange coloured oil, 6.38 g, 96%.

Ir νmax (thin film): 3300, 2940, 2863, 2130, 1730 (s), 1660 (s), 1420,1345, 1211, 1040, 956 cm⁻¹.

EXAMPLE 44

Acid A (5.0 g, 0.027 mol) and lithium hydroxide (648 mg, 0.027 mol) weredissolved in ethanol-water mixture (20 cm³) Solvents were removed invacuo to leave a white solid which was suspended in acetone. Filtration(No. 1 sinter) followed by washing of the retained solid with acetone(50 cm³) and thorough drying gave the lithium salt B 4.90 g, 96%, as awhite powder insoluble in most organic solvents.

Ir νmax (KBr Disc): 3085, 3020, 2980, 2922, 1643 (s), 1581 (s), 1422,1347, 1279, 1256, 1213, 1140, 1013, 912, 833, 808, 721, 622, 575 cm⁻¹.

EXAMPLE 45

Spermidine (5.0 g, 0.035 mol), allyl bromide (34.0 g, 0.28 mol),potassium carbonate (35.0 g) and ethanol (100 cm³) were refluxed for 6 hat 60° C. The solvent and excess allyl bromide were removed in vacuo toleave a brown oil, 21.0 g, 84%.

¹HNMR (CD₃OD) δ: 1.95 (m, 4H), 2.55 (quin, 2H), 3.45 (m, 8H), 4.0 (d,8H), 4.15 (d, 8H), 5.75 (m, 16H), 6.20 (m, 8H).

Ir νmax (thin film): 2934, 2458, 1644, 1472, 1427, 1368, 1246, 995, 953,848, 749, 662 cm⁻¹.

EXAMPLE 46

Amidoacid A (10.0 g, 0.047 mol), 3-fluorophenol (5.27 g, 0.047 mol),dicyclohexylcarbodiimide (9.70 g, 0.047 mol) and 4-dimethylaminopyridine(0.50 g) were stirred together in dry dichloromethane (150 cm³) for 18 hat room temperature. The dicyclohexylurea was removed by filtration(Whatman No. 1 filter paper) and the filtrate washed with 2M KOHsolution (100 cm³), then water (100 cm³) and dried over MgSO₄. Removalof solvent left a yellow oil which was purified by column chromatography(silica gel) using dichloromethane as the eluent. Removal of solventleft a clear oil, 13.4 g, 93.0%.

¹HNMR (CDCl₃) δ: 2.09 (t, 21H), 2.47 (t, 2H), 2.66 (t, 2H), 3.88 (d,2H), 3.99 (d, 2H), 5.20 (m, 4H), 5.78 (m, 2H), 6.90 (m, 3H), 7.40 (m,1H).

EXAMPLE 47

Itaconic anhydride (10.0 g, 0.09 mol) was placed in dry dichloromethane(150 cm3) and the mixture was cooled to −5° C. in a salt/ice bath. Thediallylamine (9.72 g, 0.10 mol) in dry dichloromethane (50 cm³) wasadded dropwise over 20 minutes, maintaining temperature>0° C. duringaddition. The mixture was stirred (during which a clear yellow solutionwas formed) for 1 hour. The solvent was removed in vacuo to leave abrown oil, 16.60 g, 89%.

Ir νmax (thin film): 2400-3400, 1717 (s), 1646 (s), 1620 (s), 1419,1220, 995, 929, 842, 555 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.35 (s, 2H), 3.92 (d, 2H), 4.10 (d, 2H), 5.2 (m, 4H),5.70 (s, 1H), 5.75 (m, 2H), 6.35 (s, 1H), 12.40 (s.v.br, 1H).

EXAMPLE 48

4-Hydroxybenzoic acid (10.0 g, 0.072 mol) and diallylamine (8.0 g, 0.082mol) were dissolved in dichloromethane/tetrahydrofuran mixture (1:1)(100 cm³). Dicyclohexylcarbodiimide (15.48 g, 0.075 mol) was addedslowly and the mixture was stirred for 72 h. The dicyclohexylurea wasremoved by filtration (Whatman No. 1 filter paper) and solvents removedto leave a brown oil. The oil was dissolved in dry dichloromethane (100cm³) and the solution washed with 3M HCl solution (100 cm³) and driedover MgSO₄. Removal of solvent left a white oily solid. Columnchromatography (silica gel/EtOAc) followed by removal of solvent, gaveafter removal of solvent in vacuo a white powder, 14.6 g, 93%.

Ir νmax (KBr disc): 3098 (br), 2932, 2809, 1640 (w), 1573, 1447, 1281,1241, 1174, 1112, 988, 936, 852, 748, 679, 636, 611, 575 cm⁻¹.

EXAMPLE 49

Citraconic anhydride (20.0 g, 0.178 mol) was dissolved in drydichloromethane (300 cm3). Diallylamine (19.4 g, 0.20 mol) in drydichloromethane (100 cm3) was added slowly dropwise over 45 minutes andstirring was continued for a further 1 h. The solvent was removed invacuo to leave a brown oil, 34.85 g, 100%.

Ir νmax (thin film): 3600-2400, 1695 (s), 1625 (s), 1415, 1263, 1200,1091, 997, 930, 798, 762, 661 cm⁻¹.

¹HNMR (CDCl₃) δ: 1.90 (s), 3.40 (d), 3.73 (d), 3.80 (d), 3.85 (d), 3.92(d), 4.95-5.15 (m), 5.18 (d), 5.22 (d), 5.29 (d), 5.55-5.92 (complex).

EXAMPLE 50

Phenylmaleic anhydride (5.0 g, 0.029 mol) was dissolved in drydichloromethane (100 cm³) and stirred. Diallylamine (3.40 g, 0.035 mol)in dry dichloromethane (20 cm³) was added slowly dropwise over 10minutes and stirring was continued for a further 1 h. The solvent wasremoved in vacuo and the residual brown oil thoroughly dried. 7.30 g,94%. The oil solidified on standing.

Ir νmax (thin film): 3600-2500, 1625 (s), 1700, 1420, 1363, 1200, 1091,997, 930, 798, 762, 660 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.60 (d, 3.70 (d), 4.10 (d), 5.0 (m), 5.20 (m), 5.45(m), 5.90 (m), 7.40 (m), 7.55 (m).

EXAMPLE 51

Gamma butyrolactone (5.00 g, 0.06 mol) and diallylamine (5.83 g, 0.06mol) were mixed together (no solvent) and heated (60° C.) for 24 h. Thinlayer chromatography (EtOAc) showed predominantly a new single productspot at ˜Rf 0.25. The reaction mixture was dissolved in drydichloromethane (100 cm³) and washed with 3N HCl (50 cm³), 3N K₂CO₃solution (50 cm;) and then brine (50 cm³). Finally, the solution wasdried over MgSO₄. The solvent was removed in vacuo and the residualbrown oil purified using column chromatography (silica gel, ethylacetate) to give after removal of solvent in vacuo, and thorough drying7.4 g, 70%, of clear oil.

¹HNMR (CDCl₃) δ: 1.90 (quin, 2H), 2.50 (t, 2H), 3.55 (s, 1H—OH), 3.66(t, 2H), 3.90 (d, 2H), 4.00 (d, 2H), 5.15 (m, 4H), 5.75 (m, 2H).

Ir νmax (thin film): 3420 (br, s), 3088, 2935, 1630 (s), 1417, 1359,1283, 1239, 1138, 1063, 995, 927 cm⁻¹.

EXAMPLE 52

6-Chlorohexan-1-ol (10.0 g, 0.073 mol), diallylamine (7.30 g, 0.075 mol)and potassium carbonate (10.37 g, 0.075 mol) were placed in ethanol (150cm³) and refluxed for 48 h. The solvent was removed in vacuo to leave abrown oil. The oil was dissolved in dichloromethane (150 cm³) and thesolution was washed in brine (100 cm³), then dried over Mgso₄. Thesolvent was removed in vacuo and the residual brown oil purified usingcolumn chromatography (silica gel—ethyl acetate). Removal of solvent invacuo gave a yellow oil, 14.7 g, 99%.

¹HNMR (CDCl₃) δ: 1.40 (m, 2H), 1.50 (quin, 2H), 1.55 (quin, 2H), 2.45(t, 2H), 2.65 (s, 1H), 3.10 (d, complex, 4H), 3.55 (t, 2H), 3.65(quartet, 2H), 5.10 (m, 4H), 5.80 (m, 2H).

Ir νmax (thin film): 3369 (s), 2964, 2934, 1517, 1459, 1374, 1300, 1243,1106, 1047, 1018, 826, 770 cm⁻¹.

EXAMPLE 53

Amide A (10.0 g, 0.055 mol) was dissolved in dry dichloromethane (100cm³) the mixture was cooled in an ice bath. Acryloyl chloride (4.95 g,0.055 mol) in dry dichloromethane (20 cm³) was added dropwise over 30minutes and the mixture was allowed to rise to room temperature. It wasleft stirring for 4 h. Thin layer chromatography (EtOAc) showed a newspot at ˜Rf 0.6. The solvent was removed in vacuo and the productpurified using column chromatography (EtOAc—40/60 petrol 1:1). Removalof solvent in vacuo gave a yellow oil 11.48 g, 89%.

Ir νmax (thin film): 2986, 1728 (s), 1645 (I), 1414, 1276, 1196, 1058,992, 929, 813, 669 cm⁻¹.

¹HNMR (CDCl₃) δ: 2.10 (m, 2H), 2.45 (m, 2H), 3.90 (d, 2H), 4.0 (d, 2H),4.2 (t, 2H), 5.20 (m, 2H), 5.75 (m, 4H), 5.80 (m, 1H), 6.15 (m, 1H),6.45 (d, 1H).

EXAMPLE 54

Benzyl chloroformate (10.0 g, 0.059 mol), diallylamine (5.85 g, 0.060mol), potassium carbonate (10.0 g) in sieve dried butanone (100 cm) werestirred together at reflux temperature for 3 h. Thin layerchromatography (ethyl aetate) showed a new spot at ˜Rf 0.5 and noevidence of diallylamine. The reaction mixture was filtered (Whatman No.1 filter paper) and solvent removed in vacuo to leave a brown oil. Theoil was purified using column chromatography (silica gel with ethylacetate as eluent). Removal of solvent in vacuo left a clear yellow oil,10.34 g, 77%.

Ir νmax (thin film): 2987, 1708 (s), 1460, 1415, 1368, 1294, 1243, 1153,1096, 995, 926, 769, 699 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.85 (d, 4H), 5. ((m, 4H), 5.14 (s, 2H), .5.75 (m, 2H).7.30 (m, 5H).

EXAMPLE 55

3-aminopropyltrimethoxysilane (10.0 g, 0.056 mol), 4-diallylamidobutyricAcid (11.8 g, 0.056 mol), dicyclohexylcarbodiimide (11.55 g, 0.056 mol)and 4-dimethylaminopyridine (0.5 g) were stirred at room temperature indry dichloromethane for 72 h. The dicyclohexylurea was removed byfiltration (Whatman No. 1 filter paper) and solvent removed to leave ayellow oil. The oil was passed through a short column of neutralaluminium followed by ethyl acetate (500 cm³). Removal of solvent left aclear colourless oil 16.8 g, 80%.

Ir νmax (thin film): 3314, 2940, 2120, 1650 (s), 1547, 1417, 1229, 1086,994, 927, 808, 754, 666 cm⁻¹.

¹HNMR (CDCl₃) δ: 0.65 (t, 2H), 1.95 (quin, 2H), 2.25 (t, 2H), 2.40 (t,2H), 3.20 (quin, 2H), 3.55 (s, 9H), 3.90 (d, 2H), 4.0 (d, 2H), 5.10 (m,4H), 5.75 (m, 2H), 6.5 (d, 2H).

EXAMPLE 56

1,4-Pentadien-3-ol (5.0 g, 0.060 mol) and acryloyl chloride (5.43 g,0.060 mol) were dissolved in dry acetone. Potassium carbonate (10 g) wasadded and the mixture was stirred at reflux for 15 h. The solids wereremoved by filtration (Whatman No. 1 filter paper) and the solventremoved in vacuo to leave a yellow oil. Chromatography using flashsilica gel with ethyl acetate as the eluent gave, after thorough dryingin vacuo, etc. 6.43 g, 78% of pale yellow oil.

Ir νmax (thin film): 2935, 1736 (s), 1653, 1618, 1411, 1186, 1090, 989,931, 810 cm⁻¹.

¹HNMR (CDCl₃) δ: 5.10-5.45 (m, 5H), 5.70-5.95 (m, 3H), 6.20 (m, 1H),6.45 (m, 1H).

EXAMPLE 57

Triallylamine (20.0 g) was dissolved in methanol and stirred at roomtemperature. 6N hexafluorophosphoric acid in methanol (from 65% solutionin H₂O) was added to pH 2.0 and the pink solution was left stirring for15 minutes. The solvents (MeOH and H₂O) were removed in vacuo to leave apink coloured oil. The oil was re-dissolved in dry dichloromethane andthe solution was dried over MgSO₄. It was then filtered (Whatman No. 1filter paper+“Hyflo”). Removal of solvent in vacuo gave a clear, pinkcoloured oil, 35.4 g, 85%.

Ir νmax (thin film): 2997, 2543, 1459, 1429, 1289, 1244, 1143, 1056,997, 953, 841 (s), 756, 661 cm⁻¹.

¹HNMR (CDCl₃) δ: 3.65 (s, 6H), 5.55 (m, 6H), 6.0 (m, 3H), 10.55 (s, br,1H).

What is claimed is:
 1. Method for producing a polymeric material, saidmethod comprising subjecting a starting material which comprises a groupof sub-formula (I)

where R¹ is CR^(a) where R^(a) is hydrogen or alkyl, and R⁶ is a bond,or R¹ and R⁶ together form an electron withdrawing group wherein either(i)R¹ is a group N⁺R¹²(Z^(m−))_(1/m), S(O)_(p)R¹³, B, P(O)_(q)R¹⁴ orSi(R¹⁵) where R¹², R¹³, R¹⁴ and R¹⁵ are independently selected fromhydrogen or hydrocarbyl, Z is an anion of charge m, p is 0, 1 or 2, andq is 1 or 2; and R⁶ is a bond; or (ii) R¹ is a nitrogen atom and R⁶ isC(O) or S(O)₂ ; or (iii) R¹ is a CH group and R⁶ is a group OC(O), C(O)or S(O)₂; R² and R³ are independently selected from (CR⁷R⁸)_(n), or agroup CR⁹R¹⁰, CR⁷R⁸CR⁹R¹⁰ or CR⁹R¹⁰CR⁷R⁸ where n is 0, 1 or 2, R⁷ and R⁸are independently selected from hydrogen or alkyl, and either one of R⁹or R¹⁰ is hydrogen and the other is an electron withdrawing group givenby nitrile, trifluoromethyl, acyl or nitro, or R⁹ and R¹⁰ together withthe carbon atom to which they are attached form an electron withdrawinggroup given by carbonyl R⁴ and R⁵ are independently selected from CH orCR¹¹ where R¹¹ is an acyl, nitrile or nitro electron withdrawing group;the dotted lines indicate the presence or absence of a bond, and X¹ is agroup CX²X³ where the dotted line bond to which it is attached is absentand a group CX² where the dotted line bond to which it is attached ispresent, Y¹ is a group CY²Y³ where the dotted line bond to which it isattached is absent and a group CY² where the dotted line bond to whichit is attached is present, and X², X³, Y² and Y³ are independentlyselected from hydrogen and fluorine; provided that at least one of (a)R¹ and R⁶ or (b) R² and R³ or (c) R⁴ and R⁵ includes an electronwithdrawing group which is able to activate a cyclopolymerizationreaction; to suitable conditions under which a cyclopolymerizationreaction will occur, subject to the following further provisos: (i) thatthe starting material is other than triallyamine hydrochloride; (ii)that when R¹ and R⁶ together form the sole electron withdrawing groupand R¹ is a group N⁺R¹²(Z^(m−))_(1/m), where R¹² is hydrogen orhydrocarbyl, Z is an anion of charge m and R⁶ is a bond, said conditionsare subjecting the compound to radiation in the substantial absence of asolvent or sulphur dioxide gas; and (iii) that where R¹ and R⁶ togetherform the sole electron withdrawing group and R¹ is CH and R⁶ is OC(O),then the compound does not further contain a mesogenic group, orcontains at least one further group of sub-formula (I).
 2. A methodaccording to claim 1 wherein the group of sub-formula (I) is a group ofsub-formula (IA)

where R¹, R², R³, R⁴, R⁵, R⁶, X², X³, Y² and Y³ are as defined inclaim
 1. 3. A method according to claim 1 wherein at least R¹ and R⁶together form an electron withdrawing group.
 4. A method according toclaim 1 wherein the conditions under which a polymerisation reactionwill occur is the application of radiation, where necessary in thepresence of a photoinitiator.
 5. A method according to claim 4 whereinthe polymerisation is effected by the application of ultraviolet orthermal radiation.
 6. A method according to claim 5 wherein theradiation is ultraviolet radiation.
 7. A method according to claim 1wherein R¹ is N⁺R¹²(Z^(m−))_(1/m), S(O)_(p)R¹³, B, P(O)_(q)R¹⁴ orSi(R¹⁵) where R¹², R¹³, R¹⁴ and R¹⁵ are independently selected fromhydrogen or hydrocarbyl, Z is an anion of charge m, p is 0, 1 or 2, andq is 1 or 2; and R⁶ is a bond.
 8. A method according to claim 7 whereinR¹ is a group N⁺R¹² (Z^(m−))_(1/m), and R⁶ is a bond.
 9. A methodaccording to claim 7 wherein Z is a halide ion, a boride ion or acarboxylic acid ester.
 10. A method according to claim 4 where R¹ is anitrogen atom and R⁶ is a group such that R¹ and R⁶ form an electronwithdrawing group.
 11. A method according to claim 10 where R¹ and R⁶together form an amide group, where R¹ is a nitrogen atom and R⁶ isC(O)—, —S(O)₂—, —C(O)O—, —CH₂O—, or a group —CH═CH—R^(a)— where R^(a) isan electron withdrawing group.
 12. A method according to claim 11wherein R⁶ is a carbonyl group or sulphonyl group.
 13. A methodaccording to claim 11 wherein R⁶ is a group —CH═CH—R^(a)— where R^(a) isa carbonyl group or phenyl substituted at the ortho and/or parapositions by an electron withdrawing substituent such as nitro.
 14. Amethod according to claim 7 wherein the conditions used to effectpolymerisation is the presence of a chemical initiator or an electronbeam.
 15. A method according to claim 1 where in the group ofsub-formula (I) X¹ and Y¹ represent CX²X³ and CY²Y³ respectively, thedotted bonds are absent and X², X³, Y² and Y³ are all hydrogen.
 16. Amethod according to claim 1 wherein the starting material is a compoundof structure (II)

where X¹, Y¹, R¹, R², R³, R⁴, R⁵, R⁶ and the dotted bonds are as definedin claim 1, r is an integer of 1 or more, and R¹⁶ is a bridging group,an optionally substituted hydrocarbyl group, a perhaloalkyl group or anamide, of valency r.
 17. A method according to claim 16 wherein thestarting material comprises a compound of formula (III)

where X¹, X² , Y¹, Y², R¹, R², R³, R¹⁴, R⁵ and R⁶ are as defined inclaim 1, R^(16′) is an optionally substituted hydrocarbyl group, aperhaloalkyl group or an amide.
 18. A method according to claim 17wherein the compound of formula (III) is a compound of formula (IV)

where R^(16′) is as defined in claim 17 or a compound of formula (VI)

where Z and m are as defined in claim 1, R²² and R²³ are independentlyselected from hydrogen and hydrocarbyl, such as alkyl and alkenyl, inparticular prop-2-enyl or hydroxyethyl.
 19. A method according to claim1 for the production of a homopolymer.
 20. A method according to claim 1when used in the production of a copolymer where the starting materialsare mixed with different monomeric units.
 21. A method according toclaim 1 wherein the starting material is applied to a substrate prior topolymerisation and the polymerisation reaction results in the productionof a coating on the substrate.
 22. A method of preparing a compound offormula (II) as defined in claim 16 which comprises reacting a compoundof formula (XV)

where X¹, Y¹, R², R³, R⁴, R⁵ and the dotted bonds are as defined inclaim 1, R^(1′) is a group R¹ as defined in claim 1 or a precursorthereof, and R⁴⁰ is hydrogen or hydroxy, with a compound of formula(XVI) R¹⁶—[R⁶—Z⁴]_(r)  (XVI) where R⁶, R¹⁶ and r is as defined inrelation to formula (II) and Z⁴ is a leaving group, and thereafter ifnecessary, converting a precursor group R^(1′) to a group R¹.
 23. Apolymer obtained by a method according to claim
 1. 24. A polymercomprising the product of a polymerisation of a compound of formula(III) as defined in claim
 17. 25. A novel compound of formula (II) asdefined in claim 16.